EP1808225B1 - Encapsulation product, process for producing the same, and ink composition - Google Patents

Encapsulation product, process for producing the same, and ink composition Download PDF

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Publication number
EP1808225B1
EP1808225B1 EP20050795833 EP05795833A EP1808225B1 EP 1808225 B1 EP1808225 B1 EP 1808225B1 EP 20050795833 EP20050795833 EP 20050795833 EP 05795833 A EP05795833 A EP 05795833A EP 1808225 B1 EP1808225 B1 EP 1808225B1
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Prior art keywords
group
pigment
polymerizable surfactant
surfactant
anionic
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German (de)
English (en)
French (fr)
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EP1808225A1 (en
EP1808225A4 (en
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Toshiyuki Seiko Epson Corporation MIYABAYASHI
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Seiko Epson Corp
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Seiko Epson Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the present invention relates to an encapsulated product, a production method thereof and an ink composition.
  • phase separation method coacervation method
  • submerged drying method interfacial precipitation method
  • spray drying method a pan coating method
  • submerged curing coating method an interfacial polymerization method
  • interfacial inorganic reaction method an in-situ polymerization method and the like
  • the core substance is limited, the thickness of the shell layer (encapsulating layer of the core substance) is hard to freely design, the encapsulation of one core substance is difficult, the functional group on the capsule surface is hard to freely design, a particle having a uniform surface state cannot be easily produced, encapsulation on the nano-order is not easy, application to a relatively unstable compound is difficult, a solvent used at the production of a preparation is readily mixed into the product, or the property of the obtained capsule is not satisfied. Also, the resulting encapsulated product itself has a problem depending on the usage.
  • an aqueous pigment ink obtained by dispersing a pigment in water has recently come to be used because of its excellent water resistance or light fastness.
  • a dispersant such as surfactant or polymer dispersant
  • the ink composition has many points to be adjusted for ensuring preferred properties as an ink, for example, there is a problem that when high printing density, fixing property or scratch resistance is intended to obtain, the viscosity tends to be high.
  • the dispersant is merely adsorbing to the pigment particle surface and in the inkjet recording method where a strong shear force is applied to the pigment particle, the dispersant adsorbing to the pigment particle surface is sometimes desorbed, as a result, the dispersibility of the pigment ink may be decreased to deteriorate the ejection stability (property that the ink is stably jetted out in a constant direction from a recording head).
  • Patent Documents 1, 2 and 3 Those prepared by encapsulating a pigment particle (see, for example, Patent Documents 1, 2 and 3) or those prepared by graft-polymerizing a polymer to the surface of a pigment particle (see, for example, Patent Documents 4 to 7) have been proposed. Also, a method of encapsulating a hydrophobic powder by using an amphipatic graft polymer has been proposed (see, for example, Patent Document 8), but this method has a problem that when a previously polymerized polymer is used for the encapsulation, the particle size after encapsulation becomes excessively large.
  • the present invention has been made by taking account of those problems and an object of the present invention is to provide an encapsulated product satisfying all of the following (1) to (8) : (1) the encapsulated coloring material particle is not limited; (2) the thickness of the shell layer (encapsulating layer of the coloring material particle) can be freely designed; (3) one coloring material particle can be encapsulated; (4 the functions of the coloring material particle and the shell substance can be separated therebetween; (5) a particle having a uniform surface state can be produced; (6) encapsulation on the nano-order is facilitated; (7) a particle having a uniform particle diameter can be produced; and (8) environment-friendly;
  • Another object of the present invention is to provide an encapsulated product satisfying all of the following (i) to (v):
  • Yet still another object of the present invention is to provide an aqueous liquid dispersion, an ink and an ink for inkjet recording each comprising the above-described encapsulated product.
  • the present invention provides:
  • the present invention also provides a method for producing an encapsulated product according to appended claim 4 and an aqueous ink composition according to appended claim 6.
  • either an inorganic material or an organic material can be used as the coloring material particle.
  • the thickness of the shell layer (encapsulating (polymer) layer of the coloring material particle) can be freely designed and at the same time, the functions of the coloring material particle and the shell substance can be separated therebetween. Moreover, a particle having a uniform surface state can be produced.
  • one coloring material particle can be encapsulated, and encapsulation on the nano-order is facilitated.
  • a particle (powder) having a uniform particle diameter can be produced.
  • the encapsulated product of the present invention can be produced by a reaction in an aqueous system using no solvent and therefore, is free from adverse effect on the environment.
  • an encapsulated product produced by using the production method of the present invention is used as a coloring material for inks, an ink having excellent dispersion stability in an aqueous liquid dispersion can be obtained. Using this ink, a recorded material excellent in the fastness and scratch resistance can be obtained. Furthermore, when an encapsulated product produced by using the production method of the present invention is used as an ink for inkjet recording, excellent ejection stability from a recording head is ensured and a recorded material having an excellent image quality can be obtained.
  • the polymer constituting the encapsulating layer for the coloring material particle can be freely designed according to the desired function, and an encapsulated product having an intended property can be easily obtained by selecting the functional group in the outermost shell.
  • the encapsulated product of the present invention is an encapsulated product comprising a coloring material particle encapsulated with a wall material mainly comprising a polymer, wherein said polymer contacts the coloring material particle through an anionic polymerizable surfactant A containing a polymerizable group, an anionic group and a hydrophobic group and comprises at least (1) a repeating structural unit derived from a cationic polymerizable surfactant B and/or cationic monomer, the cationic polymerizable surfactant B containing the cationic group, a hydrophobic group and a polymerizable group, (2) a repeating structural unit derived from an ionic polymerizable surfactant C having an electric charge the same as or opposite the electric charge of said anionic polymerizable surfactant A and containing an ionic group, a hydrophobic group and a polymerizable group, and (3) a repeating structural unit derived from a hydrophobic monomer which is present between (1) and (2); or said
  • the encapsulated product can be produced by a method comprising at least (a) a step of adsorbing an anionic polymerizable surfactant A containing an anionic group, a hydrophobic group and a polymerizable group to the surface of a coloring material particle, (b) a step of mixing and adsorbing a cationic polymerizable surfactant B and/or cationic monomer, (c) a step of adding and mixing a hydrophobic monomer, (d) a step of adding and mixing an ionic polymerizable surfactant C having an electric charge the same as or opposite the electric charge of said anionic polymerizable surfactant A, and (e) a step of performing polymerization by adding a polymerization initiator thereto; or comprising at least (a) a step of adsorbing a cationic polymerizable surfactant A containing a cationic group, a hydrophobic group and a polymerizable group to the surface of
  • an encapsulated coloring material obtained by using a coloring material particle such as pigment exhibits excellent dispersion stability in an aqueous medium and excellent ejection stability from a recording head and when an ink composition containing this encapsulated coloring material is used, an image excellent in the gloss and clarity and also excellent in the scratch resistance and fastness can be formed with high coloration on a recording medium such as plain paper and inkjet special media.
  • the present inventors have accomplished the present invention based on these findings.
  • the ionic group of the ionic surfactant adsorbed to the coloring material particle is ionically bonded to the ionic polymerizable surfactant and/or ionic monomer having an opposite electric charge
  • the hydrophobic group of the ionically bonded ionic polymerizable surfactant and/or ionic monomer faces the hydrophobic group of the ionic polymerizable surfactant having an electric charge the same as or opposite the electric charge of the ionic surfactant adsorbed to the coloring material particle
  • a structure with the ionic group of this ionic polymerizable surfactant being oriented facing toward the aqueous phase side is formed, and through a polymerization reaction in this formed state as it is, a polymer layer is formed on the coloring material particle.
  • the configuration form of the ionic surfactant, ionic polymerizable surfactant, and ionic monomer in the periphery of the coloring material particle is very highly controlled before the polymerization reaction, and a state of the ionic group being oriented toward the aqueous phase is formed in the outermost shell. Thereafter, by the polymerization reaction, the ionic polymerizable surfactant, and ionic monomer are converted into a polymer while keeping the highly controlled form, and a polymer layer is formed on the coloring material particle, whereby the encapsulated product of the present invention comes to have a highly precisely controlled structure.
  • the encapsulated product of the present invention preferably has an aspect ratio (fineness ratio) of 1.0 to 1.3 and a Zingg index of 1.0 to 1.3 (more preferably from 1.0 to 1.2).
  • the true sphere has an aspect ratio of 1 and a Zingg index of 1.
  • the shape of the encapsulated product becomes flatter and the isotropy decreases.
  • the method for adjusting the aspect ratio and the Zingg index to those ranges is not particularly limited, but the encapsulated product obtained by the above-described production method of encapsulating a core substance having a cationic group on the surface with a polymer can easily satisfy these conditions.
  • an aspect ratio and a Zingg index within the above-described ranges can be hardly obtained.
  • the encapsulated pigment of the present invention where the coloring material particle is a pigment has an aspect ratio and a Zingg index falling within those ranges and is shaped like a true sphere, whereby the flow property of an ink readily becomes Newtonian and excellent ejection stability is obtained. Also, by virtue of the true spherical shape, when the ink lands on a recording medium such as paper, the encapsulated pigment is arranged on the recording medium at a high density, and this enables to express the print density and color formation with high efficiency. Furthermore, by virtue of the true spherical shape, the pigment is also excellent in the dispersibility and dispersion stability.
  • the coloring material includes a pigment such as inorganic pigment or organic pigment capable of forming a desired color, and a dye insoluble or sparingly soluble in water, such as disperse dye and oil-soluble dye.
  • the encapsulated product can be used as a colorant for a paint, a pigment ink, or a toner.
  • one species of these coloring material particles may be used or two or more species thereof may be used in combination.
  • the coloring material which can be used in the present invention is described in more detail below.
  • the inorganic pigment examples include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black and channel black, and an iron oxide pigment.
  • the organic pigment which can be used include an azo pigment (e.g., azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment), a polycyclic pigment (e.g., phthalocyanine pigment, perylene pigment, perinone pigment, anthraquinone pigment, quinacridone pigment, dioxane pigment, thioindigo pigment, isoindolinone pigment, quinofuranone pigment), a dye chelate (e.g., basic dye-type chelate, acidic dye-type chelate), a nitro pigment, a nitroso pigment and aniline black.
  • azo pigment e.g., azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment
  • a polycyclic pigment e.g
  • Examples of the inorganic pigment which can be used as a black ink include the following carbon black: No. 2300, No. 900, MCF88, No. 33, No. 40 , No. 45, No. 52, MA 7, MA 8, MA 100 and No. 2200B (all trade names) produced by Mitsubishi Chemical Co.
  • Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255 and Raven 700 (all trade names) produced by Columbia
  • Regal 400R, Regal 330R, Regal 660R, Mogul L Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300 and Monarch 1400 (all trade names) produced by Cabot
  • Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200 Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A and Special Black 4 (all trade names) produced by Degussa.
  • a black organic pigment such as aniline black (C.I. Pigment Black 1) may be used.
  • organic yellow pigment examples include C.I. Pigment Yellow 1, C.I. Pigment Yellow 2, C.I. Pigment Yellow 3, C.I. Pigment Yellow 4, C.I. Pigment Yellow 5, C.I. Pigment Yellow 6, C.I. Pigment Yellow 7, C.I. Pigment Yellow 10, C.I. Pigment Yellow 11, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 16, C.I. Pigment Yellow 17, C.I. Pigment Yellow 24, C.I. Pigment Yellow 34, C.I. Pigment Yellow 35, C.I. Pigment Yellow 37, C.I. Pigment Yellow 53, C.I. Pigment Yellow 55, C.I. Pigment Yellow 65, C.I.
  • Pigment Yellow 73 C.I. Pigment Yellow 74, C.I. Pigment Yellow 75, C.I. Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow 98, C.I. Pigment Yellow 99, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 113, C.I. Pigment Yellow 114, C.I. Pigment Yellow 117, C.I. Pigment Yellow 120, C.I. Pigment Yellow 124, C.I.
  • organic magenta pigment examples include C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 14, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 30, C.I.
  • Pigment Red 150 C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 184, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 202, C.I. Pigment Red 209, C.I. Pigment Red 219, C.I. Pigment Red 224, C.I. Pigment Red 245, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 32, C.I. Pigment Violet 33, C.I. Pigment Violet 36, C.I. Pigment Violet 38, C.I. Pigment Violet 43 and C.I. Pigment Violet 50.
  • organic cyan pigment examples include C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:34, C.I. Pigment Blue 15:4, C.I. Pigment Blue 16, C.I. Pigment Blue 18, C.I. Pigment Blue 22, C.I. Pigment Blue 25, C.I. Pigment Blue 60, C.I. Pigment Blue 65, C.I. Pigment Blue 66, C.I. Vat Blue 4 and C.I. Vat Blue 60.
  • Examples of the organic pigment other than magenta, cyan and yellow include C.I. Pigment Green 7, C.I. Pigment Green 10, C.I. Pigment Brawn 3, C.I. Pigment Brawn 5, C.I. Pigment Brawn 25, C.I. Pigment Brawn 26, C.I. Pigment Orange 1, C.I. Pigment Orange 2, C.I. Pigment Orange 5, C.I. Pigment Orange 7, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 15, C.I. Pigment Orange 16, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43 and C.I. Pigment Orange 63.
  • a dye insoluble or sparingly soluble in water such as disperse dye and oil-soluble, dye may also be suitably used.
  • the ionic surfactant contains an ionic group and a hydrophobic group.
  • the ionic group may be either an anionic group or a cationic group, and this is appropriately selected according to the usage of the encapsulated product.
  • the anionic group is suitably, for example, an anionic group selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and a salt thereof.
  • the salt include an Na salt, a K salt, a Ca salt and an organic amine salt.
  • the cationic group is preferably a cationic group selected from the group consisting of a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation and a quaternary ammonium cation.
  • a primary ammonium cation include a monoalkylammonium cation (RNH 3 + );
  • examples of the secondary ammonium cation include a dialkylammonium cation (R 2 NH 2 + );
  • examples of the tertiary ammonium cation include a trialkylammonium cation (R 3 NH + ); and examples of the quaternary ammonium cation include (R 4 N + ).
  • R is a hydrophobic group, and examples thereof include those described below.
  • examples of the counter anion of the above-described cationic group include Cl - , Br - , I - , CH 3 OSO 3 - and C 2 H 5 OSO 3 - .
  • the hydrophobic group is preferably one species or two or more species selected from the group consisting of an alkyl group having a carbon number of 8 to 16 and an aryl group such as phenyl group and phenylene group. Also, both an alkyl group and aryl group may be contained in the molecule.
  • anionic surfactant examples include a fatty acid salt, an alkylbenzenesulfonate, an alkylnaphthalenesulfonate, an alkylsulfonate, an ⁇ -olefinsulfonate, a dialkylsulfosuccinate, an ⁇ -sulfonated fatty acid salt, an N-methyl-N-oleyltaurine, an alkylsulfonate, a sulfated fat, a polyoxyethylene alkyl ether sulfate, a polyoxyethylene alkyl phenyl ether sulfate, a polyoxyethylenestyrenated phenyl ether sulfate, an alkylphosphate, a polyoxyethylene alkyl ether phosphate, a polyoxyethylene alkyl phenyl ether phosphate and a naphthalenesulfonate formaldehyde condensate.
  • Examples of the cationic surfactant include a primary fatty amine salt, a secondary fatty amine salt, a tertiary fatty amine salt, a tetraalkylammonium salt, a trialkylbenzylammonium salt, an alkylpyridinium salt, a 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium salt, a polyethylenepolyamine fatty acid amide salt, a salt of polyethylenepolyamine fatty acid amide urea condensate, and a quaternary ammonium salt of polyethylenepolyamine fatty acid amide urea condensate.
  • the ionic polymerizable surfactant for use in the present invention is an ionic surfactant containing the above-described ionic group and hydrophobic group and further containing a polymerizable group.
  • the polymerizable group is preferably a polymerizable group selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group and a vinylene group.
  • an allyl group, a methacryloyl group and an acryloyl group are preferred.
  • the hydrophobic group is preferably one species or two or more species selected from the group consisting of an alkyl group having a carbon number of 8 to 16 and an aryl group such as phenyl group and phenylene group. Also, both an alkyl group and aryl group may be contained in the molecule.
  • the ionic group may be either an anionic group or a cationic group, and this is appropriately selected according to the usage of the encapsulated product.
  • the ionic polymerizable surfactant is referred to as an anionic polymerizable surfactant or a cationic polymerizable surfactant depending on whichever of an anionic group or a cationic group is contained as the ionic group.
  • the anionic polymerizable surfactant for use in the present invention is an anionic surfactant containing an anionic group and a hydrophobic group and further containing a polymerizable group.
  • the anionic group is suitably, for example, an anionic group selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and a salt thereof.
  • the salt include an Na salt, a K salt, a Ca salt and an organic amine salt.
  • the hydrophobic group is preferably one species or two or more species selected from the group consisting of an alkyl group having a carbon number of 8 to 16 and an aryl group such as phenyl group and phenylene group. Also, both an alkyl group and aryl group may be contained in the molecule.
  • the polymerizable group is preferably an unsaturated hydrocarbon group capable of radical polymerization.
  • the polymerizable group is preferably a group selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group and a vinylene group.
  • an allyl group, a methacryloyl group and an acryloyl group are preferred.
  • anionic polymerizable surfactant examples include anionic allyl derivatives described in JP-B-49-46291 , JP-B-1-24142 and JP-A-62-104802 ; anionic propenyl derivatives described in JP-a-62-221431 ; anionic acrylic acid derivatives described in JP-A-62-34947 and JP-A-55-11525 ; and anionic itaconic acid derivatives described in JP-B-46-34898 and JP-A-51-30284 .
  • the anionic polymerizable surfactant for use in the present invention is preferably, for example, a compound represented by the following formula (31): [wherein R 21 and R 31 each is independently a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 12, Z 1 is a carbon-carbon single bond or a group represented by the formula: -CH 2 -O-CH 2 -, m is an integer of 2 to 20, X is a group represented by the formula: -SO 3 M 1 , and M 1 is an alkali metal, an ammonium salt or an alkanolamine], or a compound represented by the following formula (32): [wherein R 22 and R 32 each is independently a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 12, D is a carbon-carbon single bond or a group represented by the formula: -CH 2 -O-CH 2 -, n is an integer of 2 to 20, Y is a group represented by the formula: -SO 3 M 2 , and M 2 is
  • Examples of the anionic polymerizable surfactant represented by formula (31) include the compounds described in - JP-A-5-320276 and JP-A-10-316909 .
  • the hydrophilicity on the surface of the encapsulated coloring material particle obtained by encapsulating a coloring material particle can be adjusted by appropriately selecting the number of m in formula (31).
  • the polymerizable surfactant represented by formula (31) is preferably a compound represented by the following formula (310), and specific examples thereof include the compounds represented by the following formulae (31a) to (31d). [wherein R 31 , m and M 1 are the same as those in the compound represented by formula (31)].
  • the anionic polymerizable surfactant for use in the present invention is preferably, for example, a compound represented by formula (33): [wherein p is 9 or 11, q is an integer of 2 to 20, A is a group represented by -SO 3 M 3 , and M 3 is an alkali metal, an ammonium salt or an alkanolamine].
  • the anionic polymerizable surfactant represented by formula (33) is preferably a compound shown below. [wherein r is 9 or 11, and s is 5 or 10].
  • AQUALON KH Series (AQUALON KH-5 and AQUALON KH-10) (all are trade names) produced by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • AQUALON KH-5 is a mixture of a compound where in the compound represented by formula (33), r is 9 and s is 5, and a compound where r is 11 and s is 5, and
  • AQUALON KH-10 is a mixture of a compound where r is 9 and s is 10, and a compound where r is 11 and s is 10.
  • the anionic polymerizable surfactant for use in the present invention is preferably a compound represented by the following formula (34): [wherein R is an alkyl group having a carbon number of 8 to 15, n is an integer of 2 to 20, X is a group represented by -SO 3 B, and B is an alkali metal, an ammonium salt or an alkanolamine].
  • ADEKA REARSOPE SR Series (ADEKA REARSOPE SR-10, SR-20 and SR-1025) (all trade names) produced by Asahi Denka Co., Ltd.
  • ADEKA REARSOPE SR Series is a compound where in formula (34), B is NH 4 .
  • anionic polymerizable surfactant for use in the present invention, a compound represented by the following formula (A) may also be used.
  • R 4 represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 12, 1 represents a number of 2 to 20, and M 4 represents an alkali metal, an ammonium salt or an alkanolamine].
  • anionic polymerizable surfactant a commercially available product may also be used.
  • the commercially available product include AQUALON HS Series (AQUALON HS-10, HS-20 and HS-1025) (all are trade names) produced by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • anionic polymerizable surfactant for use in the present invention includes, for example, a sodium alkylallylsulfosuccinate represented by formula (35).
  • anionic polymerizable surfactant a commercially available product may also be used.
  • the anionic polymerizable surfactant for use in the present invention includes, for example, a sodium methacryloyloxy polyoxyalkylene sulfate represented by formula (36).
  • n is a number of 1 to 20.
  • anionic polymerizable surfactant for use in the present invention for example, a compound represented by formula (37) may be used.
  • this anionic polymerizable surfactant a commercially available product may also be used, and Antox MS-60 produced by Nippon Nyukazai Co., Ltd. comes under this surfactant.
  • anionic polymerizable surfactants may be used alone or two or more species thereof may be used as a mixture.
  • the cationic polymerizable surfactant for use in the present invention is a cationic surfactant containing a cationic group and a hydrophobic group and further containing a polymerizable group.
  • the cationic group is preferably a cationic group selected from the group consisting of a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation and a quaternary ammonium cation.
  • Examples of the primary ammonium cation include a monoalkylammonium cation (RNH 3 + );
  • examples of the secondary ammonium cation include a dialkylammonium cation (R 2 NH 2 + ) ;
  • examples of the tertiary ammonium cation include a trialkylammonium cation (R 3 NH + ); and examples of the quaternary ammonium cation include (R 4 N + ).
  • R is a hydrophobic group, and examples thereof include those described below.
  • the hydrophobic group is preferably one species or two or more species selected from the group consisting of an alkyl group having a carbon number of 8 to 16 and an aryl group such as phenyl group and phenylene group. Also, both an alkyl group and aryl group may be contained in the molecule.
  • Examples of the counter anion of the above-described cationic group include Cl - , Br - , I - , CH 3 OSO 3 - and C 2 H 5 OSO 3 - .
  • the polymerizable group is preferably an unsaturated hydrocarbon group capable of radical polymerization.
  • the polymerizable group is preferably a group selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group and a vinylene group.
  • an allyl group, a methacryloyl group and an acryloyl group are preferred.
  • the cationic polymerizable surfactant includes, for example, a compound represented by the formula: R [4-(1+m+n)] R 1 l R 2 m R 3 n N + ⁇ X - (wherein R is a polymerizable group, R 1 , R 2 and R 3 each is an alkyl group having a carbon number of 8 to 16 or an aryl group such as phenyl group or phenylene group, X - is Cl - , Br - , I - , CH 3 OSO 3 - or C 2 H 5 OSO 3 - , and l, m and n each is 1 or 0).
  • examples of the polymerizable group include those described above.
  • cationic polymerizable surfactant examples include a dimethylaminoethylmethacrylate octyl chloride salt, a dimethylaminoethylmethacrylate cetyl chloride salt, a dimethylaminoethylmethacrylate decyl chloride salt, a dimethylaminoethylmethacrylate dodecyl chloride salt and a dimethylaminoethylmethacrylate tetradecyl chloride salt.
  • One of these cationic polymerizable surfactants may be used alone, or two or more species thereof may be used as a mixture.
  • the nonionic polymerizable surfactant contains a nonionic group, a hydrophobic group and a polymerizable group.
  • nonionic group examples include a hydroxyl group, a polyoxyethylene group and a polyglycerin group.
  • the hydrophobic group is preferably one species or two or more species selected from the group consisting of an alkyl group having a carbon number of 8 to 16 and an aryl group such as phenyl group and phenylene group. Also, both an alkyl group and aryl group may be contained in the molecule.
  • the polymerizable group is preferably an unsaturated hydrocarbon group capable of radical polymerization.
  • the polymerizable group is preferably a group selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group and a vinylene group.
  • an allyl group, a methacryloyl group and an acryloyl group are preferred.
  • the hydrophobic group and the polymerizable group include the same as those described above.
  • nonionic polymerizable surfactant a compound represented by the following formula (100) may be used. [wherein R 50 represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 12, and n represents a number of 5 to 50].
  • a commercially available product may also be used.
  • the commercially available product include AQUALON RN Series (AQUALON RN-10, RN-20, RN-30, RN-50 and RN-2025) (all are trade names) produced by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • the following formula (101) shows AQUALON RN-20.
  • nonionic polymerizable surfactant a compound represented by the following formula (103) may be used. [wherein R 51 represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 12, and n represents a number of 5 to 50].
  • nonionic polymerizable surfactant a commercially available product may also be used.
  • the commercially available product include NOIGEN Series (NOIGEN N-10, N-20, N-30 and N-50) (all are trade names) produced by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • the following formula (104) shows NOIGEN N-20.
  • nonionic polymerizable surfactant a compound represented by the following formula (105) may be used. [wherein R 52 is an alkyl group having a carbon number of 8 to 15, and n is an integer of 5 to 50].
  • a commercially available product may also be used.
  • the commercially available product include ADEKA REARSOPE ER Series (ADEKA REARSOPE ER-10, ER-20, ER-30 and ER-40) (all trade names) produced by Asahi Denka Co., Ltd.
  • nonionic polymerizable surfactant a compound represented by the following formula (106) may be used. [wherein R 53 represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 12, and n is a number of 5 to 50].
  • a commercially available product may also be used.
  • the commercially available product include ADEKA REARSOPE NE Series (ADEKA REARSOPE NE-5, NE-10, NE-20, NE-30 and NE-40) (all trade names) produced by Asahi Denka Co., Ltd.
  • nonionic polymerizable surfactant examples include poly(ethylene glycol-propylene glycol) monomethacrylate (trade name: BLEMMER 50PEP-300 ⁇ produced by NOF Corp.>, formula (108)), polyethylene glycol polypropylene glycol monomethacrylate (trade name: BLEMMER 70PEP-350B ⁇ produced by NOF Corp.>, formula (109)), polyethylene glycol polypropylene glycol monoacrylate (trade name: SLIMMER AEP Series ⁇ produced by NOF Corp.>), poly(ethylene glycol-tetramethylene glycol) monoacrylate (trade name: BLEMMER AET Series ⁇ produced by NOF Corp.>), poly(propylene glycol-tetramethylene glycol) monoacrylate (trade name: BLEMMER APT Series ⁇ produced by NOF Corp.>), lauroxy polyethylene glycol monomethacrylate (trade name: BLEMMER PLE-200 ⁇ produced by NOF Corp.>, formula (110)), lauroxy polyethylene
  • the ionic monomer for use in the present invention is a compound containing an ionic group and a polymerizable group and is water-soluble.
  • the ionic group may be either an anionic group or a cationic group, and this is appropriately selected according to the usage of the encapsulated product.
  • the anionic group is suitably, for example, an anionic group selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and a salt thereof.
  • the salt include an Na salt, a K salt, a Ca salt and an organic amine salt.
  • the cationic group is preferably a cationic group selected from the group consisting of a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation and a quaternary ammonium cation.
  • the primary ammonium cation include a monoalkylammonium cation (RNH 3 + );
  • examples of the secondary ammonium cation include a dialkylammonium cation (R 2 NH 2 + ) ;
  • examples of the tertiary ammonium cation include a trialkylammonium cation (R 3 NH + ) ; and examples of the quaternary ammonium cation include (R 4 N + ).
  • R is a hydrophobic group, and examples thereof include those described below.
  • examples of the counter anion of the above-described cationic group include Cl - , Br - , I - , CH 3 OSO 3 - and C 2 H 5 OSO 3 - .
  • the ionic monomer is referred to as an anionic water-soluble monomer or a cationic water-soluble monomer depending on whichever of an anionic group or a cationic group is contained as the ionic group.
  • a commercially available product may also be used.
  • ACRYESTER DMC Mitsubishi Rayon Co., Ltd.
  • ACRYESTER DML60 Mitsubishi Rayon Co., Ltd.
  • C-1615 Dai-ichi Kogyo Seiyaku Co., Ltd.
  • One of these cationic water-soluble monomers may be used alone, or two or more species thereof may be used as a mixture.
  • examples of the monomer having a carboxyl group include an acrylic acid, a methacrylic acid, a crotonic acid, a propylacrylic acid, an isopropylacrylic acid, a 2-acryloyloxyethylsuccinic acid, a 2-acryloyloxyethylphthalic acid, a 2-methacryloyloxyethylsuccinic acid, a 2-methacryloyloxyethylphthalic acid, an itaconic acid, a fumaric acid and a maleic acid.
  • an acrylic acid and a methacrylic acid are preferred.
  • Examples of the monomer having a sulfonic acid group include a 4-styrenesulfonic acid including a salt thereof, a vinylsulfonic acid including a salt thereof, a sulfoethyl acrylate including a salt thereof, a sulfoethyl methacrylate including a salt thereof, a sulfoalkyl acrylate including a salt thereof, a sulfoalkyl methacrylate including a salt thereof, a sulfopropyl acrylate including a salt thereof, a sulfopropyl methacrylate including a salt thereof, a sulfoaryl acrylate including a salt thereof, a sulfoaryl methacrylate including a salt thereof, a butyl-acrylamidesulfonic acid including a salt thereof, and a 2-acrylamido-2-methylpropanesulfonic acid including a salt thereof.
  • Examples of the monomer having a phosphonic group include a phosphoric acid group-containing (meth)acrylate such as phosphoethyl methacrylate.
  • a phosphoric acid group-containing (meth)acrylate such as phosphoethyl methacrylate.
  • anionic water-soluble monomers may be used alone, or two or more species thereof may be used as a mixture.
  • the ionic polymerizable surfactant A for use in the present invention is used for the purpose of adsorbing it to a coloring material particle, and the ionic group may be either anionic or cationic.
  • the ionic polymerizable surfactant A for use in the present invention is the same as those described above in the items of Ionic Polymerizable Surfactant, Anionic Polymerizable Surfactant and Cationic Polymerizable Surfactant.
  • the ionic polymerizable surfactant B for use in the present invention has an electric charge opposite the electric charge of the ionic surfactant a and/or the ionic polymerizable surfactant A.
  • anionic polymerizable surfactant and cationic polymerizable surfactant used as the ionic polymerizable surfactant B for use in the present invention are the same as those described above in the items of Ionic Polymerizable Surfactant, Anionic Polymerizable Surfactant and Cationic Polymerizable Surfactant.
  • the ionic polymerizable surfactant C for use in the present invention has an electric charge the same as or opposite the electric charge of the ionic surfactant a and/or the ionic polymerizable surfactant A.
  • anionic polymerizable surfactant and cationic polymerizable surfactant used as the ionic polymerizable surfactant C for use in the present invention are the same as those described above in the items of Ionic Polymerizable Surfactant, Anionic Polymerizable Surfactant and Cationic Polymerizable Surfactant.
  • the nonionic polymerizable surfactant D is the same as those described above in the item of Nonionic Polymerizable Surfactant.
  • the nonionic group of the nonionic polymerizable surfactant D is present in the outermost layer of the encapsulated product.
  • a nonionic surfactant e may be used in combination and allowed to adsorb to the coloring material particle surface together with the ionic polymerizable surfactant A.
  • This nonionic surfactant e contains a nonionic group and a hydrophobic group, and examples of the nonionic group include a hydroxyl group, a polyoxyethylene group and a polyglycerin group.
  • the hydrophobic group is preferably one species or two or more species selected from the group consisting of an alkyl group having a carbon number of 8 to 16 and an aryl group such as phenyl group and phenylene group. Also, both an alkyl group and aryl group may be contained in the molecule.
  • nonionic surfactant e examples include a polyethylene glycol alkyl ether such as polyethylene glycol lauryl ether, polyethylene glycol tridecyl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether and polyethylene glycol oleyl ether, a polyethylene glycol nonylphenyl ether, a polyethylene glycol octylphenyl ether, a polyethylene glycol monolaurate, a polyethylene glycol monostearate, a polyethylene glycol monooleate, a sorbitan monolaurate, a sorbitan monomyristate, a sorbitan monopalmitate, a sorbitan monostearate, a sorbitan monooleate, a sorbitan trioleate, a polyethylene glycol sorbitan monolaurate, a polyethylene glycol sorbitan monostearate, a polyethylene glycol sorbitan monostearate,
  • a nonionic surfactant E may be used in combination and allowed to adsorb to the coloring material particle surface together with the ionic polymerizable surfactant A.
  • the nonionic polymerizable surfactant E is the same as those described in the item of Nonionic Polymerizable Surfactant.
  • the hydrophobic monomer as used in the present invention means a polymerizable monomer containing at least a hydrophobic group and a polymerizable group in its structure, and examples thereof include those containing a hydrophobic group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
  • Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group and a propyl group; examples of the alicyclic hydrocarbon group include a cyclohexyl group, a dicyclopentenyl group, a dicyclopentanyl group and an isobornyl group; and examples of the aromatic hydrocarbon group include a benzyl group, a phenyl group and a naphthyl group.
  • the usable polymerizable group of the hydrophobic monomer is the same as those described above in the item of Ionic Polymerizable Surfactant.
  • hydrophobic monomer examples include styrene derivatives such as styrene, methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, tert-butylstyrene, bromostyrene and p-chloromethylstyrene; monofunctional acrylic esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, butoxyethyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, benzyl acrylate, phenyl acrylate, phenoxyethyl acrylate, cyclo
  • the film-forming property of the encapsulated product of the present invention and the strength, chemical resistance, water resistance, light fastness, weather resistance, optical property, physical property and chemical property of the encapsulating film are determined by the structure of hydrophobic monomer, and the structure of copolymer comprising a hydrophobic monomer. Accordingly, the hydrophobic monomer may be selected according to the performance required of the encapsulated product. For example, when the encapsulated product of the present invention using a coloring material is used as a recording material, the recorded matter can be made to have the required fixing property or scratch resistance by controlling the glass transition point (Tg) of the copolymer with which the coloring material particle is encapsulated.
  • Tg glass transition point
  • a state where a very large force is required for slight deformation abruptly changes into a state where large deformation is caused with a small force.
  • the temperature at which this phenomenon occurs is called a glass transition point (or a glass transition temperature).
  • a differential thermal curve obtained by measuring the temperature rise by means of a differential scanning calorimeter, the temperature at an intersection of a tangential line drawn from a bottom of a heat absorption peak to an initiation point of heat absorption and a base line is generally taken as the glass transition point.
  • the glass transition point can be calculated according to the Fox formula from the weight fraction of a monomer used for the synthesis of a copolymer and the glass transition point of a homopolymer obtained by homopolymerizing the monomer.
  • Tg [p] is a glass transition temperature of the obtained polymer
  • i is a number affixed every different kinds of monomers
  • Tg [hp]i is a glass transition temperature of the homopolymer of the monomer i used for the polymerization
  • x is the weight fraction of the monomer i based on the total weight of the monomers polymerized).
  • the copolymer when the temperature in the environment where the encapsulated product of the present invention is placed is higher than the glass transition point of the copolymer with which the coloring material particle of the encapsulated product of the present invention is encapsulated, the copolymer enters a state where large deformation is caused with a small force, and when the temperature further reaches the melting point, the copolymer melts. At this time, when other encapsulated products are present in the vicinity, the encapsulated products are fuse-bonded with each other to form a film.
  • the encapsulated product of the present invention using a coloring material is used as an ink for inkjet recording
  • a recording medium such as plain paper or special recording medium for inkjet recording
  • an aqueous medium comprising water and/or a water-soluble organic solvent present in the periphery of the encapsulated particle of the present invention penetrates into the plain paper or special recording medium for inkjet recording and disappears from the vicinity of the encapsulated particle, as a result, the encapsulated particles come near each other.
  • the glass transition point (Tg) of the copolymer covering the coloring material particle of the encapsulated particle is not higher than room temperature, the copolymers covering the coloring particles are fuse-bonded by the effect of a capillary pressure generated in the gap between the encapsulated particles, thereby forming a film with the coloring material being embraced (included) inside.
  • the glass transition point of the copolymer covering the coloring material particle of the encapsulated product of the present invention is preferably 30°C or less, more preferably 15°C or less, still more preferably 10°C or less.
  • the encapsulated product more successfully forms a film at room temperature.
  • the copolymer covering the coloring material particle of the encapsulated product is preferably designed to have a glass transition point of 30°C or less, more preferably 15°C or less, still more preferably 10°C or less.
  • the glass transition point is less than -20°C, the solvent resistance tends to decrease and therefore, careful design is demanded.
  • a hydrophobic monomer satisfying these required properties is appropriately selected, and the amount added thereof is arbitrarily determined.
  • the encapsulated product of the present invention using a coloring material is used as a toner
  • the glass transition point (Tg) of the copolymer covering the coloring material particle of the encapsulated particle is set to be not higher than the fixing temperature
  • the copolymers covering the coloring particles are fuse-bonded, and a film with the coloring material being embraced (included) inside is formed on the plain paper which is a recording medium, so that fixing property of the colorant to the recording medium and scratch resistance can be obtained.
  • the glass transition point of the copolymer covering the coloring material particle of the encapsulated product of the present invention is preferably not lower than a temperature having no adverse effect on the electrophotographic process except for the fixing process, particularly, on the development process, and transfer process.
  • a hydrophobic monomer satisfying the properties required as the physical toner properties such as film-forming property, strength of encapsulating film, electrical property, chemical resistance, water resistance, light fastness, weather resistance and optical property, is appropriately selected, and the amount added thereof is arbitrarily determined.
  • a monomer represented by the following formula (2) may be further used within the range of not impairing the effect of the present invention.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a tert-butyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group
  • m represents an integer of 0 to 3
  • n represents an integer of 0 to 1
  • examples of the alicyclic hydrocarbon group represented by R 2 include a cycloalkyl group, a cycloalkenyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group and an adamantane group, and examples of the heterocyclic group include a tetrahydrofuran group.
  • the R 2 group which is a "bulky” group derived from the monomer represented by formula (2) is incorporated into the polymer of the capsule wall material, this enables to decrease the deflection of the polymer molecule, that is, decrease the mobility of the molecule and thereby enhance the mechanical strength and heat resistance of the polymer. Therefore, with use of an ink composition containing the encapsulated coloring material of the present invention using a coloring material particle, a printed matter excellent in the weather resistance and durability can be obtained. Furthermore, by virtue of causing the R 2 group which is a "bulky” group to exist in the polymer constituting the capsule wall material, the organic solvent in the ink composition can be prevented from penetrating into the polymer and therefore, the encapsulated coloring material can have excellent solvent resistance.
  • the dispersibility of the coloring material particle in the ink composition for inkjet recording where a water-soluble organic solvent is present together, as well as the storage stability of the ink composition and the ejection property of the ink composition from an inkjet head can be enhanced.
  • the polymer having a repeating structural unit derived from a monomer having a long-chain alkyl group out of the above-described monomers has flexibility. Accordingly, when the ratio of the repeating structural unit derived from a crosslinking monomer described later and/or the repeating structural unit derived from the monomer represented by formula (2) to the repeating structural unit derived from the monomer having a long-chain alkyl group is appropriately adjusted, a capsule wall material polymer having high mechanical strength and excellent solvent resistance in combination with preferred plasticity can be synthesized.
  • the ink composition containing an encapsulated coloring material particle encapsulated with such a polymer is excellent in the dispersion stability, long-term storage stability and ejection stability from an inkjet head, even if a water-soluble organic solvent is contained therein. Also, when the ink composition containing such an encapsulated coloring material particle is used for printing, the image of the printed matter is assured of good fixing property to a recording medium such as paper or inkjet special media. Furthermore, this ink composition can provide an image excellent in the scratch resistance, durability and solvent resistance.
  • the encapsulated product of the present invention comprises a coloring material particle encapsulated with a material mainly comprising a polymer and, in addition to the above-described various surfactants, polymerizable surfactants and hydrophobic monomers, other polymerizable monomer components may be used as the raw material.
  • examples of other polymerizable monomers usable in the present invention include a crosslinking monomer. When a crosslinking monomer is added to the polymerization components and copolymerized with the hydrophobic monomer, the mechanical strength and heat resistance of the polymer can be increased to enhance the shape retentivity of the capsule wall material.
  • the swelling of the polymer due to an organic solvent or the penetration of an organic solvent into the polymer can be prevented, and the solvent resistance of the capsule wall material can be elevated.
  • the dispersibility of the coloring material particle in the ink composition for inkjet recording where a water-soluble organic solvent is present together, as well as the storage stability of the ink composition and the ejection property of the ink composition from an inkjet head can be enhanced.
  • the crosslinking monomer for use in the present invention includes a compound having two or more unsaturated hydrocarbon groups of at least one species selected from a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group and a vinylene group.
  • crosslinking monomer examples include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, allyl acrylate, bis(acryloxyethyl)hydroxyethyl isocyanurate, bis(acryloxyneopentyl glycol) adipate, 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis[4-(acryloxy)phenyl]propane, 2,2-bis[4-(acryloxyethoxy)phenyl]propane, 2,2-bis[4-(acryloxy-ethoxy-diethoxy)phenyl]propane, 2,2-bis[4-(acryloxy-ethoxy ⁇ polyethoxy
  • the polymer having a repeating structural unit derived from this crosslinking monomer or the polymer having a repeating structural unit derived from the monomer represented by formula (2) is advantageous in that the glass transition temperature (Tg) is high and the mechanical strength, heat resistance and solvent resistance are excellent.
  • the amount used of the crosslinking monomer and/or the monomer represented by formula (2) is preferably adjusted to an appropriate amount.
  • the polymer constituting the capsule wall material of the encapsulated product of the present invention is obtained, as described above, by polymerizing an ionic polymerizable surfactant, an ionic monomer and a hydrophobic monomer.
  • This polymerization reaction can be performed by using a known polymerization initiator. Particularly, use of a radical polymerization initiator is preferred.
  • a polymerization initiator suitable for the polymerization method employed is preferably used.
  • the polymerization initiator is preferably a water-soluble polymerization initiator, and examples thereof include persulfate (e.g., potassium persulfate, ammonium persulfate, sodium persulfate), hydrogen peroxide, 2,2-azobis(2-methylpropionamidine) dihydrochloride, and 4,4-azobis(4-cyanovaleric acid).
  • persulfate e.g., potassium persulfate, ammonium persulfate, sodium persulfate
  • hydrogen peroxide 2,2-azobis(2-methylpropionamidine) dihydrochloride
  • 4,4-azobis(4-cyanovaleric acid 4,4-azobis(4-cyanovaleric acid
  • a redox-type initiator combining an oxidizing agent such as potassium persulfate, ammonium persulfate, sodium persulfate and hydrogen peroxide, with a reducing agent such as sodium sulfite, sodium hyposulfite, ferrous sulfate, ferrous nitrate and thiourea, may be used.
  • an oxidizing agent such as potassium persulfate, ammonium persulfate, sodium persulfate and hydrogen peroxide
  • a reducing agent such as sodium sulfite, sodium hyposulfite, ferrous sulfate, ferrous nitrate and thiourea
  • an oil-soluble azo compound-based initiator such as dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis(2-methylbutyronitrile), or an oil-soluble polymerization initiator such as peroxide (e.g., dilauroyl peroxide, disuccinic acid peroxide, 1,1,3,3-tetramethylbutyl(peroxy-2-ethylhexanoate) and 2,5-dimethyl-2,5-di(2-ethyl-hexanoylperoxy)hexane, is preferably used.
  • peroxide e.g., dilauroyl peroxide, disuccinic acid peroxide, 1,1,3,3-tetramethylbutyl(peroxy-2-ethylhexanoate) and 2,5-dimethyl-2,5-di(2-ethyl-hexanoylper
  • the encapsulated product of the present invention comprises a core member encapsulated with a material mainly comprising a polymer and, in addition to those described above as the raw material, other components such as ultraviolet absorbent, light stabilizer, antioxidant, flame retardant, plasticizer and wax, may be incorporated into the polymer.
  • the capsule wall material of the encapsulated product is synthesized by a polymerization reaction, and this polymerization reaction is preferably performed by using a reaction vessel equipped with an ultrasonic wave generator, a stirrer, a reflux condenser, a dropping funnel and a temperature regulator.
  • the encapsulated product according to the embodiment of the present invention is suitably produced, specifically, by the following procedure.
  • an ionic polymerizable surfactant A containing a polymerizable group, an ionic group and a hydrophobic group is adsorbed to the surface of a coloring material particle. More specifically, it is preferred to charge the coloring material particle into an ion-exchanged water having dissolved therein the ionic surfactant A and after mixing, subject the mixed solution to a dispersion treatment in a general dispersing device such as ball mill, roll mill, Eiger mill or jet mill, thereby sufficiently adsorbing the ionic surfactant A to the coloring material particle.
  • a general dispersing device such as ball mill, roll mill, Eiger mill or jet mill
  • the ionic surfactant A not adsorbed to the core substance is preferably removed by filtration. If the unadsorbed ionic surfactant is remaining in a large amount, the amount of a polymer particle produced as a by-product increases and this gives rise to insufficient encapsulation of the coloring material particle. However, if the unadsorbed ionic surfactant is excessively removed, the dispersion of the coloring material particle sometimes becomes unstable. Therefore, an appropriate degree of ultrafiltration is preferably determined by taking account of the dispersion stability and the condition of encapsulation.
  • an ionic polymerizable surfactant B and/or ionic monomer having an electric charge opposite the electric charge of the ionic surfactant A is added and mixed to the liquid dispersion of the coloring material particle having adsorbed thereto the ionic surfactant A.
  • an ultrasonic wave is preferably irradiated on the mixture so as to facilitate the ionic bonding of the ionic group of the ionic polymerizable surfactant B and/or ionic monomer to the ionic group of the ionic polymerizable surfactant A.
  • the amount of the ionic polymerizable surfactant B and/or ionic monomer having an electric charge opposite the electric charge of the ionic surfactant A, added to the liquid dispersion of the coloring material particle having adsorbed thereto the ionic surfactant A is preferably from 0.5 to 2 molar times, more preferably from 0.8 to 1.2 molar times, based on the total molar number of the ionic group of the ionic surfactant A (that is, the amount [mol/g] of the ionic group present on the surface of 1 g of the coloring material particle used).
  • the ionic polymerizable surfactant B and/or ionic monomer having an opposite electric charge in an amount of 0.5 molar times or more based on the total molar amount of the ionic group of the ionic surfactant A adsorbed to the surface of the coloring material particle, an encapsulated produce with good dispersibility can be obtained through the subsequent polymerization reaction. This is considered to result because the ionic polymerizable surfactant B and/or ionic monomer can satisfactorily cover the coloring material particle.
  • the amount of the ionic polymerizable surfactant B and/or ionic monomer added is 2 molar times or less, the generation of a polymer particle having no coloring material particle (a particle comprising only a polymer) can be suppressed.
  • a hydrophobic monomer is added.
  • the timing of adding the hydrophobic monomer may be after (IV).
  • a monomer selected from the group consisting of a crosslinking monomer, a compound represented by formula (2) and other known polymerizable monomers may be used in combination.
  • an ionic polymerizable surfactant C having an electric charge the same as or opposite the electric charge of the ionic surfactant A is added and mixed.
  • the amount of the ionic polymerizable surfactant C added is preferably from 0.5 to 10 molar times, more preferably from 0.5 to 5 molar times, based on the ionic polymerizable surfactant B and/or ionic monomer.
  • this amount added is 0.5 molar times or more, the aggregation of the encapsulated product can be suppressed and an encapsulated product liquid dispersion having excellent dispersion stability can be obtained.
  • the amount added is 10 molar times or less, the amount of the ionic polymerizable surfactant C not contributing to the encapsulation of the coloring material particle can be decreased and the generation of a polymer particle can be suppressed.
  • the ionic polymerizable surfactant B and/or ionic monomer having an electric charge opposite the electric charge of the ionic surfactant A electrostatically adheres to the surface of the coloring material particle having adsorbed thereto the ionic polymerizable surfactant A, the hydrophobic monomer is localized on the outer side thereof depending on the case, and the ionic polymerizable surfactant C having an electric charge the same as or opposite the electric charge of the ionic group of the ionic surfactant A is oriented on the further outer side thereof, with the ionic group facing the aqueous phase side, whereby an admicell is formed.
  • a nonionic polymerizable surfactant D may be used in combination, if desired.
  • the amount of the nonionic polymerizable surfactant added is adjusted such that the total of this amount and the amount of the ionic polymerizable surfactant C added becomes from 0.5 to 10 molar times, preferably from 0.5 to 5 molar times, based on the ionic polymerizable surfactant B and/or ionic monomer.
  • the ratio between the nonionic polymerizable surfactant D and the ionic polymerizable surfactant C is appropriately selected according to the property required of the encapsulated product obtained.
  • the ultrasonic irradiation is not necessarily required.
  • a polymerization initiator is added to the mixed solution prepared as above to perform a polymerization reaction.
  • the polymerization initiator may be added en bloc or in parts at a temperature high enough to activate the polymerization initiator or may be added continuously.
  • the mixed solution may be heated to a temperature high enough to active the polymerization initiator.
  • the reaction can be more suitably performed by dissolving a water-soluble polymerization initiator in ion-exchanged water and adding dropwise the obtained aqueous solution to an aqueous liquid dispersion in a reaction vessel at a predetermined dropping speed.
  • the reaction can be suitably performed by adding the polymerization initiator as it is or after dissolving it in the hydrophobic monomer.
  • the polymerization initiator may be suitably activated by elevating the temperature of the system to a temperature high enough to cause cleavage of the polymerization initiator and generation of an initiator radical.
  • the polymerization initiator is cleaved to generate an initiator radical, and this radial attacks the polymerizable group of the ionic polymerizable surfactant or the polymerizable group of the ionic monomer and hydrophobic monomer, whereby a polymerization reaction takes place.
  • the polymerization temperature and the polymerization reaction time vary depending on the kind of the polymerization initiator used and the kind of the above-described polymerizable compound, but it is easy to appropriately set preferred polymerization conditions.
  • the polymerization temperature is preferably from 40 to 90°C, and the polymerization time is preferably from 3 to 12 hours.
  • the ionic surfactant A and the ionic polymerizable surfactants B and C used, and the hydrophobic monomer, the crosslinking monomer, the compound represented by formula (2) and other known polymerizable monomers, which are used, if desired, each may be used as one species or in combination of two or more species.
  • the polymerization reaction is performed by using an ionic polymerizable surfactant, the mixed solution has a good emulsified state in many cases even without using an emulsifier. Therefore, use of an emulsifier is not necessarily required, but, if desired, at least one member selected from the group consisting of known anionic, nonionic and cationic emulsifiers may be used.
  • the obtained aqueous liquid dispersion of the encapsulated product of the present invention is preferably adjusted to a pH of 7.0 to 9.0 and further filtered.
  • the filtration is preferably ultrafiltration.
  • an ionic polymerizable surfactant A containing a polymerizable group, an ionic group and a hydrophobic group is first adsorbed to the surface of a coloring material particle. Then, an ionic polymerizable surfactant B having an electric charge opposite the electric charge of the ionic surfactant A and/or an ionic monomer having an electric charge opposite the electric charge of the ionic surfactant A is considered to be adsorbed.
  • a polymerizable monomer including a hydrophobic monomer is added (as described above, the polymerizable monomer including a hydrophobic monomer may be added after an ionic polymerizable surfactant C is added), and an ionic polymerizable surfactant C having an electric charge the same as or opposite the electric charge of the ionic group of the ionic surfactant A is further added and mixed.
  • the configuration form of ionic polymerizable surfactants and polymerizable monomer molecules present in the periphery of the coloring material particle is very highly controlled, and the ionic group (anionic group or cationic group) in the outermost layer is considered to form an oriented state toward the aqueous phase side.
  • a polymer having at least a repeating structural unit derived from the ionic polymerizable surfactant B and a repeating structural unit derived from the ionic polymerizable surfactant C is considered to be formed around the coloring material particle, whereby the encapsulated product of the present invention is obtained.
  • a polymer having a repeating structural unit derived from the ionic polymerizable surfactant B, a repeating structural unit derived from the ionic polymerizable surfactant C and a repeating structural unit comprising the hydrophobic monomer is formed around the coloring material particle. Furthermore, according to the polymerization method of the present invention, the production of a water-soluble oligomer or polymer as a by-product is suppressed.
  • the aqueous liquid dispersion of the encapsulated product obtained by using the polymerization method of the present invention is low in the viscosity and assured of excellent dispersibility and excellent dispersion stability. This is considered to result because, as described above, the ionic group (anionic group or cationic group) in the outermost layer of the encapsulated product is forming a highly oriented state toward the aqueous phase side.
  • an ink composition for inkjet recording using the encapsulated product obtained by the polymerization method of the present invention with use of a coloring material particle is excellent in the dispersion stability and ejection stability from a recording head and less blurred even on plain paper, so that a printed image with high color formation and high density can be obtained.
  • the encapsulated product obtained by using the polymerization method of the present invention allows for introduction of a functional group such as ionic group or nonionic group in a highly oriented state into the outermost layer, so that by utilizing such a functional group, a functional group having a peculiar function can be further introduced with ease.
  • a composite functionality fine particle having several peculiar functions at the same time can be obtained.
  • the encapsulated product of the present invention obtained in this way has high dispersion stability in an aqueous solvent, and this is considered attributable to the fact that the coloring material particle is completely covered by a polymer layer (an uncovered portion is not present) and at the same time, the hydrophilic group in the polymer layer of the capsule wall material is regularly oriented toward an aqueous solvent.
  • the production method of the encapsulated product of the present invention is again described by specifically referring, as an example, to a case where a pigment as a coloring material particle is used.
  • a pigment is charged into an ion-exchanged water having dissolved therein an anionic polymerizable surfactant and after mixing, the mixed solution is subject to a dispersion treatment in a general dispersing device such as ball mill, roll mill, Eiger mill or jet mill, thereby adsorbing the anionic polymerizable surfactant to the pigment particle surface. Thereafter, the anionic polymerizable surfactant not adsorbed to the pigment particle is removed by ultrafiltration. At this time, if the unadsorbed anionic polymerizable surfactant is excessively removed, the dispersion of the pigment sometimes becomes unstable. Therefore, the degree of ultrafiltration is appropriately determined by taking account of the dispersion stability and the condition of encapsulation.
  • a cationic polymerizable surfactant and/or a cationic water-soluble monomer is added and mixed to this liquid dispersion comprising the pigment having adsorbed thereto the anionic polymerizable surfactant.
  • an ultrasonic wave is preferably irradiated on the mixture so as to facilitate the ionic bonding of the cationic group of the cationic polymerizable surfactant and/or the cationic water-soluble monomer to the anionic group of the anionic polymerizable surfactant.
  • the amount of the cationic polymerizable surfactant and/or the cationic water-soluble monomer added to the pigment liquid dispersion is preferably from 0.5 to 2 molar times, more preferably from 0.8 to 1.2 molar times, based on the total molar number of the ionic group of the anionic polymerizable surfactant adsorbed to the pigment (that is, the amount [mol/g] of the ionic group present on the pigment surface of 1 g of the pigment particle).
  • the cationic polymerizable surfactant and/or the cationic water-soluble monomer By adding the cationic polymerizable surfactant and/or the cationic water-soluble monomer in an amount of 0.5 molar times or more based on the total molar amount of the anionic group of the anionic polymerizable surfactant adsorbed to the pigment particle surface, an encapsulated pigment with good dispersibility can be obtained through the subsequent polymerization reaction.
  • the amount of the cationic polymerizable surfactant and/or the cationic water-soluble monomer added is 2 molar times or less, the generation of a polymer particle (a particle comprising only a polymer) can be suppressed.
  • a hydrophobic monomer is added and mixed.
  • a monomer selected from the group consisting of a crosslinking monomer, a compound represented by formula (2) and other known polymerizable monomers may be used in combination.
  • the timing of adding such a hydrophobic monomer may be after the addition of an anionic polymerizable surfactant described later.
  • an anionic polymerizable surfactant is added and mixed.
  • the amount of the anionic polymerizable surfactant added is preferably from 0.5 to 10 molar times, more preferably from 0.5 to 5 molar times, based on the cationic polymerizable surfactant and/or the cationic water-soluble monomer.
  • this amount added is 0.5 molar times or more, the aggregation of the encapsulated pigment particle can be suppressed and a pigment liquid dispersion having excellent dispersion stability can be obtained.
  • the ink composition using the obtained pigment liquid dispersion exhibits excellent ejection stability from an inkjet recording head and enhanced adsorptivity to paper fiber and gives high print density and high color formation.
  • the amount added is 10 molar times or less, the amount of the anionic polymerizable surfactant not contributing to the encapsulation of the pigment particle can be decreased and the generation of a polymer particle can be suppressed.
  • a polymerization initiator is added to the mixed solution prepared as above to perform a polymerization reaction.
  • the polymerization initiator may be added en bloc or in parts to the mixed solution heated at a temperature high enough to activate the polymerization initiator or may be added continuously. Also, after the addition of the polymerization initiator, the mixed solution may be heated to a temperature high enough to active the polymerization initiator.
  • the polymerization initiator either a water-soluble polymerization initiator or an oil-soluble polymerization initiator may be used, but in the case of using a water-soluble polymerization initiator, the polymerization initiator is preferably dissolved in pure water and added dropwise to the mixed solution in a reaction vessel.
  • the reaction can be suitably performed by adding the polymerization initiator as it is or after dissolving it in the hydrophobic monomer.
  • the polymerization temperature and the polymerization reaction time vary depending on the kind of the polymerization initiator used and the kind of the polymerizable monomer, but it is easy for one skilled in the art to appropriately set preferred polymerization conditions. In general, the polymerization temperature is preferably from 40 to 90°C, and the polymerization time is preferably from 3 to 12 hours.
  • the obtained aqueous liquid dispersion of the encapsulated pigment of the present invention is preferably adjusted to a pH of 7.0 to 9.0 and further filtered.
  • the filtration is preferably ultrafiltration.
  • an ionic polymerizable surfactant and a polymerizable monomer molecule take a very high configuration form in the periphery of a pigment particle, and the outermost layer is in such a state that an anionic group is densely oriented toward the aqueous phase.
  • an encapsulated pigment where the periphery of a pigment particle is covered with a polymer in a highly controlled form can be obtained.
  • the production of a water-soluble oligomer or polymer as a by-product is suppressed.
  • the encapsulated pigment obtained in the present invention has a form such that a pigment particle is covered with a polymer which is a capsule wall material, and when an antioxidant, and a plasticizer are added, if desired, to the mixed solution before polymerization or during polymerization reaction, these additives may be incorporated into the polymer.
  • a polymer which is a capsule wall material
  • an antioxidant, and a plasticizer are added, if desired, to the mixed solution before polymerization or during polymerization reaction, these additives may be incorporated into the polymer.
  • known materials may be used.
  • the encapsulated pigment of the present invention is preferably purified before use by previously removing the unreacted material (for example, the polymerizable compound used such as ionic polymerizable surfactant and hydrophobic monomer).
  • the amount of the unreacted material contained in the encapsulated pigment liquid dispersion is preferably 50,000 ppm or less, more preferably 10,000 ppm or less.
  • a centrifugal separation method, and an ultrafiltration method may be used. The above-described amount of the unreacted material can be easily measured by using gas chromatography or liquid chromatography.
  • an image printed on plain paper can have excellent color saturation and high printing density (print density) and there is also obtained an effect that the generation of blurring of the image is suppressed. Furthermore, an image printed on special media for inkjet recording, particularly, on inkjet gloss media, can have higher gloss.
  • the particle diameter of the encapsulated pigment is preferably 400 nm or less, more preferably 300 nm or less, still more preferably from 20 to 200 nm (the particle diameter of the encapsulated pigment can be measured, for example, by using a commercially available dynamic light-scattering particle size distribution analyzer or laser Doppler system particle size distribution analyzer).
  • the glass transition temperature (Tg) of the polymer as a main component of the capsule wall material for the encapsulated pigment of the present invention is preferably 30°C or less, more preferably 15°C or less.
  • a desired glass transition temperature can be obtained by selecting the monomer used and selecting the ratio of monomers used.
  • the glass transition temperature of the polymer can be estimated, as described above, by using the Fox formula.
  • the Tg of the polymer as the main component of the capsule wall material is 30°C or less, the encapsulated coloring materials are readily joined with each other on a recording medium, and this advantageously enables to more enhance the scratch resistance of the image and increase the adhesion to a recording medium.
  • the Tg is still more preferably 10°C or less.
  • the ink composition using the encapsulated pigment obtained by the above-described production method is low in the viscosity and assured of excellent dispersibility and excellent dispersion stability and particularly when used as an ink composition for inkjet recording, excellent ejection stability from a recording heat is ensured, so that a printed image with high color formation and high density can be obtained on plain paper and a printed image with high gloss and high clarity can be obtained on special media for inkjet recording.
  • the encapsulated coloring material obtained can be used for an ink composition and is preferably used particularly as a coloring material of an ink for inkjet recording.
  • the coloring particle is preferably a pigment.
  • the ink composition for inkjet recording using an encapsulated pigment where a pigment is used as the coloring material particle in the encapsulated coloring material obtained by the present invention, is described below.
  • the ink composition for inkjet recording of the present invention is an aqueous ink composition where the above-described encapsulated pigment is contained in the dispersed state in an aqueous medium.
  • the encapsulated pigment content in the ink composition is preferably from 1 to 20 wt%, more preferably from 3 to 15 wt%, based on the entire weight of the ink composition. For obtaining high print density and high color formation, this content is still more preferably from 5 to 15 wt%.
  • the solvent for use in the ink composition of the present invention preferably comprises water and a water-soluble organic solvent and may contain other components, if desired.
  • a wetting agent comprising a high boiling point water-soluble organic solvent is preferably added to the ink composition of the present invention.
  • the high boiling point water-soluble organic solvent is preferably a water-soluble organic solvent having a boiling point of 180°C or more.
  • water-soluble organic solvent having a boiling point of 180°C or more which can be used in the present invention, include ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol, polyethylene glycol having a molecular weight of 2,000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, glycerin, mesoerythritol and pentaerythritol.
  • the boiling point of the high boiling point water-soluble organic solvent for use in the present invention is more preferably 200°C or more.
  • one of these high boiling point water-soluble organic solvents may be used alone, or two or more species thereof may be used.
  • an ink for inkjet recording capable of maintaining flowability and re-dispersibility for a long period of time even when allowed to stand in an open state (a state such that the ink composition is in contact with air at room temperature), can be obtained.
  • an ink composition scarcely causes clogging of an inkjet nozzle during printing in an inkjet printer or at the restarting after interruption of printing, so that an ink composition assured of high ejection stability from an inkjet nozzle can be obtained.
  • the total content of the water-soluble organic solvent including the high boiling point water-soluble organic solvent is preferably on the order of 10 to 50 wt%, more preferably from 10 to 30 wt%, based on the entire weight of the ink composition.
  • the ink composition of the present invention may further contain one or more polar solvent selected from the group consisting of 2-pyrrolidone, N-methylpyrrolidone, ⁇ -caprolactam, dimethyl sulfoxide, sulfolane, morpholine, N-ethylmorpholine and 1,3-dimethyl-2-imidazolidinone.
  • polar solvent selected from the group consisting of 2-pyrrolidone, N-methylpyrrolidone, ⁇ -caprolactam, dimethyl sulfoxide, sulfolane, morpholine, N-ethylmorpholine and 1,3-dimethyl-2-imidazolidinone.
  • the content of such a polar solvent is preferably from 0.1 to 20 wt%, more preferably from 1 to 10 wt%, based on the entire weight of the ink composition.
  • the ink composition of the present invention preferably further contains a penetrant.
  • a penetrant By virtue of prompt penetration of the aqueous solvent into the recording medium, a recorded matter having a less blurred image can be obtained.
  • an alkyl ether of a polyhydric alcohol (also called glycol ethers) and/or a 1,2-alkyldiol is preferably used.
  • alkyl ether of a polyhydric alcohol examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-tert-butyl ether, propylene glycol mono-methyl
  • 1,2-alkyldiol examples include 1,2-pentanediol and 1,2-hexanediol.
  • Other examples include diols of a linear hydrocarbon, such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol.
  • An appropriate penetrant may be selected from these and used in the ink composition of the present invention.
  • At least one member selected from propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 1,2-pentanediol and 1,2-hexanediol is preferably used as the penetrant.
  • the penetrant content is, in terms of the total amount, preferably from 1 to 20 wt%, more preferably from 1 to 10 wt%, based on the entire weight of the ink composition.
  • the penetrant content is 1 wt% or more, an effect of enhancing the penetrability of the ink composition into the recording medium is obtained, and when the content is 20 wt% or less, generation of blurring on the image printed by using this ink composition can be prevented and excessive increase in the viscosity of the ink composition can be suppressed.
  • a 1,2-alkyldiol such as 1,2-pentanediol and 1,2-hexanediol is used in the ink composition, good drying property of the ink composition after printing can be obtained and blurring of the image can be reduced.
  • glycerin when glycerin is incorporated into the ink composition of the present invention, clogging of an inkjet nozzle on using the ink composition for inkjet recording is less generated, and the storage stability of the ink composition itself may also be enhanced.
  • glycol ethers in the ink composition of the present invention, an acetylene glycol-based surfactant described later is preferably used in combination with the glycol ethers.
  • the ink composition of the present invention preferably contains a surfactant, particularly an anionic surfactant and/or a nonionic surfactant.
  • a surfactant particularly an anionic surfactant and/or a nonionic surfactant.
  • the anionic surfactant include an alkanesulfonate, an ⁇ -olefinsulfonate, an alkylbenzenesulfonate, an alkylnaphthalenesulfonic acid, an acylmethyltaurine acid, a dialkylsulfosuccinic acid, an alkylsulfuric ester salt, a sulfated oil, a sulfated olefin, a polyoxyethylene alkyl ether sulfuric ester salt, a fatty acid salt, an alkyl sarcosine salt, an alkylphosphoric ester salt, a polyoxyethylene alkyl ether phosphoric ester salt and a monoglyceride phosphoric ester
  • nonionic surfactant examples include a polyoxyethylene alkyl ether, a polyoxyethylene alkyl phenyl ether, a polyoxyethylene alkyl ester, a polyoxyethylene alkylamide, a glycerin alkyl ester, a sorbitan alkyl ester, a sugar alkyl ester, a polyhydric alcohol alkyl ether, and an alkanolamine fatty acid amide.
  • examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium laurate and an ammonium salt of a polyoxyethylene alkyl ether sulfate
  • examples of the nonionic surfactant include an ether-based compound such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether and polyoxyalkylene alkyl ether, and an ester-based compound such as polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearic acid ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate and polyoxyethylene
  • the ink for inkjet recording preferably contains, as the surfactant, an acetylene glycol-based surfactant and/or an acetylene alcohol-based surfactant.
  • the surfactant an acetylene glycol-based surfactant and/or an acetylene alcohol-based surfactant.
  • n each is a number satisfying 0 ⁇ m+n ⁇ 50
  • R 1 , R 2 , R 3 and R 4 each is independently an alkyl group (preferably an alkyl group having a carbon number of 6 or less).
  • Particularly preferred examples of the compound represented by formula (6) include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol and 3,5-dimethyl-1-hexyn-3-ol.
  • a commercial product available as an acetylene glycol-based surfactant on the market may also be used as the compound represented by formula (6).
  • Specific examples thereof include Surfynol 104, 82, 465, 485, 104PG50 and TG (all are trade names, available from Air Products and Chemicals, Inc.); and Olfine STG and Olfine E1010 (both are trade names, produced by Nissin Chemical Industry Co., Ltd.).
  • Examples of the commercial product as the acetylene alcohol-based surfactant include Surfynol 61 (trade name, available from Air Products and Chemicals, Inc.).
  • Such an acetylene glycol-based surfactant and/or acetylene alcohol-based surfactant is preferably used to account for 0.01 to 10 wt%, more preferably from 0.1 to 5 wt%, based on the entire weight of the ink composition.
  • the pigment particle when the pigment particle is encapsulated with a capsule wall material mainly comprising a polymer having a crosslinked structure derived from a crosslinking monomer, a polymer having a repeating structural unit derived from the monomer represented by formula (2), or a polymer having both of these in the structure, high mechanical strength, heat resistance and solvent resistance may be obtained, but the plasticity of the polymer tends to become insufficient, causing reduction in the fixing property of the coloring material to the recording medium or the scratch resistance.
  • the fixing property and scratch resistance can be compensated for.
  • the fine polymer particle for use in the ink composition of the present invention preferably has, on the surface thereof, the same species of ionic group as the ionic group on the surface of the encapsulated pigment of the present invention and has a glass transition point of 30°C or less and a volume average particle diameter of 10 to 100 nm.
  • the above-described fine polymer particle has a film-forming property and when the ink composition of the present invention containing this fine polymer particle is printed on a recording medium such as plain paper or special media for inkjet recording, the solvent component (including water) in the ink composition penetrates into the recording medium, as a result, the polymer particle and the encapsulated pigment particle come near each other, and the polymer particle forms a polymer film to embrace the encapsulated pigment particle.
  • the encapsulated pigment in the ink can be more firmly fixed on the recording medium surface, so that an image having very excellent resistance against scratches and water can be formed.
  • the glass transition temperature of the polymer is preferably 30°C or less, more preferably 15°C or less, still more preferably 10°C or less.
  • the glass transition temperature of the polymer can be adjusted by appropriately selecting the kind or compositional ratio of the monomers used.
  • a glass transition temperature obtained by measuring the temperature rise by means of a differential scanning calorimeter (DSC) is used as the glass transition temperature of the polymer.
  • This fine polymer particle does not cause aggregation even when present together with the encapsulated pigment particle of the present invention in the ink composition, and a good dispersed state is obtained.
  • the particle diameter of the fine polymer particle is from 10 to 100 nm in terms of the volume average particle diameter, an image having good gloss and high clarity is obtained.
  • the fine polymer particle preferably comprises a polymer containing at least from 1 to 10 wt% of a repeating unit derived from an ionic group-containing unsaturated vinyl monomer, more preferably a polymer containing from 1 to 10 wt% of a repeating unit derived from an ionic group-containing unsaturated vinyl monomer, having a structure crosslinked with a crosslinking monomer having two or more polymerizable double bonds, and containing from 0.2 to 4 wt% of a structure derived from this crosslinking monomer.
  • crosslinking monomers having two or more, preferably three or more, polymerizable double bonds are copolymerized with another polymerizable monomer at the polymerization, thereby crosslinking the polymer chains, and a fine polymer particle comprising such a crosslinked polymer is used for the ink composition
  • the surface of a nozzle plate of an inkjet recording device becomes more difficult to wet with the ink composition, so that the ink droplet can be prevented from flight bending and the ejection stability can be enhanced.
  • the fine polymer particle for use in the present invention can be produced by a known emulsion polymerization method.
  • an unsaturated vinyl monomer is emulsion-polymerized in water in the presence of a polymerization initiator and an emulsifier, whereby the fine polymer particle can be obtained.
  • the unsaturated vinyl monomer those the same as the above-described hydrophobic monomer may be used.
  • the polymerization initiator, emulsifier, surfactant, molecular-adjusting agent, neutralizer and the like used at the production of the fine polymer particle are used according to a known method.
  • anionic polymerizable surfactant since the anionic polymerizable surfactant is copolymerized with the monomer, the amount of the emulsifier in the liquid becomes small and in turn, bubbling in the liquid is suppressed, as a result, the ejection stability of the ink composition is more enhanced.
  • the same anionic polymerizable surfactant as that used for the encapsulated pigment of the present invention is used, the dispersion stability and the storage stability become remarkably excellent.
  • the fine polymer particle may be used as a fine particle power, but a polymer emulsion prepared by dispersing the fine polymer particle in a water medium is preferably mixed with other components contained in the ink composition.
  • the amount of the fine polymer particle contained in the ink composition is preferably on the order of 0.01 to 10 wt%, more preferably on the order of 0.01 to 5 wt%, based on the entire weight of the ink composition.
  • the ink composition of the present invention may contain a pH adjusting agent.
  • the pH of the ink composition is preferably adjusted to 7 to 11, more preferably from 8 to 9, and a basic compound is preferably used as the pH adjusting agent.
  • the pH of the ink composition is preferably adjusted to 5 to 7, more preferably from 6 to 7, and an acidic compound is preferably used as the pH adjusting agent.
  • the basic compound preferred as the pH adjusting agent include alkali metal salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, lithium carbonate, sodium phosphate, potassium phosphate, lithium phosphate, potassium dihydrogenphosphate, dipotassium hydrogenphosphate, sodium oxalate, potassium oxalate, lithium oxalate, sodium borate, sodium tetraborate, potassium hydrogenphthalate and potassium hydrogentartrate; ammonia; and amines such as methylamine, ethylamine, diethylamine, trimethylamine, triethylamine, tris(hydroxymethyl)aminomethane hydrochloride, triethanolamine, diethanolamine, diethylethanolamine, triisopropenolamine, butyldiethanolamine, morpholine and propanolamine.
  • alkali metal salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium hydrogencarbon
  • the dispersion stability of the anionic group-containing pigment particle in the ink can be enhanced.
  • a benzoic acid a dichlorophene, a hexachlorophene, a sorbic acid, a p-hydroxybenzoic acid ester, an ethylenediaminetetraacetic acid (EDTA), a sodium dehydroacetate, a 1,2-benthiazolin-3-one [product name: Proxel XL (produced by Avecia)],
  • At least one member selected from the group consisting of urea, thiourea and ethylene urea may also be added to the ink composition of the present invention.
  • One particularly preferred embodiment of the ink composition according to the present invention is, for example, an ink composition comprising at least:
  • an ink composition comprising at least:
  • the amount added thereof is preferably 10 wt% or less, more preferably from 0.5 to 5 wt%, based on the entire weight of the ink composition.
  • the penetrability of the ink composition into the recording medium can be increased and this is useful for the enhancement of printing quality.
  • diethylene glycol monobutyl ether and/or triethylene glycol monobutyl ether has an effect of increasing the solubility of an acetylene glycol-based surfactant.
  • the amount added thereof is preferably 15 wt% or less based on the entire weight of the ink composition. If a 1,2-alkyldiol having a carbon number of 3 or less is used, sufficiently high penetrability of the ink composition into the recording medium cannot be obtained. Also, a 1,2-alkyldiol having a carbon number of more than 15 is difficult to dissolve in water and this is not preferred.
  • 1,2-alkyldiol in the ink composition exceeds 15 wt%, the viscosity of the ink composition disadvantageously tends to be increased.
  • 1,2-alkyldiol specifically, 1,2-pentanediol or 1,2-hexanediol is preferably used, and either one may be used alone or both may be used in combination.
  • the 1,2-pentanediol is preferably added in an amount of 3 to 15 wt% based on the entire weight of the ink composition. By adding 1,2-pentanediol in an amount of 3 wt% or more to the ink composition, an ink composition with good penetrability is obtained.
  • the 1,2-hexanediol is preferably added in an amount of 0.5 to 10 wt% based on the entire weight of the ink composition, and within this range, an ink composition with good penetrability is obtained.
  • a solid wetting agent is preferably added in an amount of 3 to 20 wt% based on the entire weight of the ink composition.
  • the addition of a solid moisture-retaining agent is not limited to the embodiments described above, but the solid wetting agent may be added to an ink composition using the encapsulated pigment of the present invention.
  • the solid wetting agent means a water-soluble substance which is solid at ordinary temperature (25°C) and has a water-retaining function.
  • Preferred examples of the solid wetting agent include saccharides, sugar alcohols, hyaluronate, trimethylolpropane and 1,2,6-hexanetriol.
  • sugar examples include a monosaccharide, a disaccharide, an oligosaccharide (including a trisaccharide and a tetrasaccharide) and a polysaccharide, and among these sugars, preferred are glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol, sorbit, maltose, cellobiose, lactose, sucrose, trehalose and maltotriose.
  • polysaccharides as used herein means a sugar in its broad sense and is used as the meaning of including substances widely occurring in nature, such as alginic acid, ⁇ -cyclodextrin and cellulose.
  • the derivative of such saccharides includes a reduced sugar of the above-described saccharides (for example, a sugar alcohol represented by the formula: HOCH 2 (CHOH) n CH 2 OH (wherein n represents an integer of 2 to 5)), an oxidized sugar (for example, an aldonic acid and a uronic acid), an amino acid and a thiosugar.
  • sugar alcohols are preferred, and specific examples thereof include maltitol, sorbitol and xylitol.
  • hyaluronate those commercially available as an aqueous 1% sodium hyaluronate solution (molecular weight: 350,000) may be used.
  • these solid wetting agents more preferred are trimethylolpropane, 1,2,6-hexanetriol, saccharides and sugar alcohols.
  • One species or two or more species of these solid wetting agents may be added in the ink composition of the present invention.
  • the solid wetting agent When the solid wetting agent is used in the ink composition, the evaporation of water of the ink can be suppressed by the water retaining function, so that increase in the viscosity of the ink composition does not occur in the ink flow path of an inkjet printer or in the vicinity of an inkjet nozzle, and film formation due to evaporation of water of the ink composition and in turn clogging of a nozzle hardly occur. Also, the above-described solid wetting agent is chemically stable and therefore, does not decompose in the ink composition, so that the quality of the ink composition can be maintained for a long period of time.
  • the nozzle plate is not wetted with the ink composition and stable ejection of the ink composition from an inkjet nozzle can be attained.
  • the amount of the solid wetting agent added in the ink composition of the present invention is, in terms of the total amount, preferably from 3 to 20 wt%, more preferably from 3 to 10 wt%, based on the entire weight of the ink composition.
  • the combination thereof is preferably a combination of one or more member selected from saccharides, sugar alcohols and a hyaluronate and one or more member selected from trimethylolpropane and 1,2,6-hexanetriol.
  • the ink composition When the amount of the solid wetting agent contained in the ink composition is 3 wt% or more, an effect of preventing clogging of the inkjet nozzle can be obtained, and when the amount of the solid wetting agent contained in the ink composition is 20 wt% or less, the ink composition can be stably ejected from the inkjet nozzle and therefore, an ink composition having sufficiently low viscosity can be obtained.
  • an acetylene glycol-based surfactant and/or an acetylene alcohol-based surfactant of (3) is added to the ink composition, and the total amount of these surfactants is preferably from 0.01 to 10 wt%, more preferably from 0.1 to 5 wt%, based on the entire weight of the ink composition.
  • the ink composition in each of the above-described embodiments ensures particularly high dispersion stability of pigment and excellent ejection stability form an inkjet head nozzle when used for an inkjet recording method and enables stable printing without clogging of nozzles for a long period of time. Furthermore, when this ink composition is printed on a recording medium such as plain paper, recycled paper and coated paper, good drying property of the ink after printing is ensured. By using this ink composition, a high-quality image with no blurring, high print density and excellent color formation can be obtained.
  • the present invention is described above and there are the following differences between an ink composition prepared by using the encapsulated pigment of the present invention and an ink composition prepared by using a conventionally known pigment.
  • a dispersant such as surfactant and polymer dispersant
  • acetylene glycol-based surfactant and/or acetylene alcohol-based surfactant and a penetrant such as diethylene glycol monobutyl ether
  • the ink composition obtained by the present invention can be stably ejected through an inkjet nozzle for a long period of time.
  • the encapsulated pigment particle obtained by the present invention has good solvent resistance and this hardly allows for desorption of the polymer of the capsule wall material from the pigment particle surface, or swelling of the polymer due to the penetrant, so that the stably dispersion of the pigment particle in the ink composition can be maintained for a long time.
  • the viscosity of the ink composition tends to be high due to the dispersant dissolved in the pigment liquid dispersion, because in general, the dispersant is not entirely adsorbed to the pigment surface at the initial stage after dispersing the pigment in a liquid dispersion medium. Furthermore, the dispersant desorbs from the pigment with the passing of time after the dispersion of pigment and due to this desorbed dispersant, the viscosity of the ink composition tends to be high. Therefore, the pigment content in the pigment liquid dispersion cannot be increased in many cases.
  • the ink composition using the encapsulated pigment obtained by the present invention is advantageous in that low viscosity can be easily attained and a larger number of pigment particles can be contained, and even when plain paper or recycled paper is used as the printing medium, a sufficiently high print density can be obtained.
  • the encapsulated pigment obtained by the present invention is shaped like a true sphere and therefore, the flow property of the ink composition using this pigment readily becomes Newtonian. This is considered attributable to the fact that the ionic group on the encapsulated pigment surface is regularly and densely oriented toward the aqueous solvent side and an effective electrostatic repulsive force is generated between the encapsulated pigments. Therefore, as compared with conventional encapsulated pigments, the ink composition using the encapsulated pigment obtained by the present invention exhibits excellent ejection stability from the inkjet head in the inkjet recording method.
  • an ink composition for inkjet recording increased in the concentration of the colorant contained can be produced and by using this ink composition, an image having a high print density can be obtained.
  • the ink composition obtained by the present invention is particularly preferred as an ink composition for use in an inkjet recording method.
  • the ink composition prepared by using the micro-encapsulated pigment of the present invention preferably further comprises a compound represented by the following formula (1):
  • R 1 and R 2 each independently represents an alkyl group having a carbon number of 1 to 10, m and n each represents a number of repeating units, and m+n is from 0 to 10 on average).
  • R 1 and R 2 each is independently an alkyl group having a carbon number of 1 to 10, m and n each is a number of repeating units, and m+n is from 0 to 10 on average, but in order to obtain an aqueous ink composition ensuring that an ink giving less blurring and high color formation on plain paper and having fixing property on special paper in addition to sufficiently high color formation can be prepared and excellent ejection stability and a satisfactory line width at printing can be further secured in the inkjet recording, the carbon number of R 1 +R 2 is preferably from 5 to 15, and m+n is preferably from 0 to 7.
  • the content of the compound represented by formula (1) in the ink composition comprising the compound is preferably from 0.1 to 20 wt%, more preferably from 0.3 to 10 wt%, based on the entire weight of the ink composition. In order to obtain good gloss and high image clarity, the content is still more preferably from 0.5 to 10 wt%.
  • the anionic polymerizable surfactant, AQUALON KH-10 (produced by Dai-ichi Kogyo Seiyaku Co., Ltd.), used in Examples is a compound represented by the following formula:
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until AQUALON KH-10/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 1.5 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 120 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 33°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until dimethylaminoethylmethacrylate methyl chloride salt/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 4.6 g of potassium persulfate as a polymerization initiator in 200 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 120 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 25°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until AQUALON KH-10/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 1.5 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 180 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 46°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until dimethylaminoethylmethacrylate octyl chloride salt/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 3.6 g of potassium persulfate as a polymerization initiator in 200 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 120 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 46°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until AQUALON KH-10/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 1.5 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 120 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 33°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until dimethylaminoethylmethacrylate dodecyl chloride salt/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 3.6 g of potassium persulfate as a polymerization initiator in 200 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 120 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 46°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until AQUALON KH-10/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 2 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 200 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 33°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • an anionic polymerizable surfactant ADEKA REARSOPE SR-10 (produced by Asahi Denka Co., Ltd.)
  • ADEKA REARSOPE SR-10 produced by Asahi Denka Co., Ltd.
  • 100 g of an isoindolinone pigment C.I. Pigment Red 122
  • the resulting mixed solution was subjected to a dispersion treatment for 5 hours by using a disperser, Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan Co., Ltd.), under the conditions of a bead loading of 70% and a rotation number of 5,000 rpm.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until ADEKA REARSOPE SR-10/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 1.5 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 160 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 33°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • an anionic polymerizable surfactant ELEMINOL JS-2 (produced by Sanyo Chemical Industries, Ltd.)
  • ELEMINOL JS-2 produced by Sanyo Chemical Industries, Ltd.
  • 100 g of an isoindolinone pigment C.I. Pigment Red 122
  • the resulting mixed solution was subjected to a dispersion treatment for 5 hours by using a disperser, Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan Co., Ltd.), under the conditions of a bead loading of 70% and a rotation number of 5,000 rpm.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until ELEMINOL JS-2/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 1.8 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 160 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 33°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • an anionic polymerizable surfactant ADEKA REARSOPE SE-10N (produced by Asahi Denka Co., Ltd.)
  • ADEKA REARSOPE SE-10N produced by Asahi Denka Co., Ltd.
  • 100 g of an isoindolinone pigment C.I. Pigment Red 122
  • the resulting mixed solution was subjected to a dispersion treatment for 5 hours by using a disperser, Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan Co., Ltd.), under the conditions of a bead loading of 70% and a rotation number of 5,000 rpm.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until ADEKA REARSOPE SE-10N/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 1.0 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 160 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 33°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • an anionic polymerizable surfactant ELEMINOL RS-30 (produced by Sanyo Chemical Industries, Ltd.)
  • ELEMINOL RS-30 produced by Sanyo Chemical Industries, Ltd.
  • 100 g of an isoindolinone pigment C.I. Pigment Red 122
  • the resulting mixed solution was subjected to a dispersion treatment for 5 hours by using a disperser, Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan Co., Ltd.), under the conditions of a bead loading of 70% and a rotation number of 5,000 rpm.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until ELEMINOL RS-30/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 1.5 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 160 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 33°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • an anionic polymerizable surfactant Antox MS-60 (produced by produced by Nippon Nyukazai Co., Ltd.), was dissolved in 850 g of ion-exchanged water, and 100 g of C.I. Pigment Blue 15:4 was added thereto and mixed.
  • the resulting mixed solution was subjected to a dispersion treatment for 5 hours by using a disperser, Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan Co., Ltd.), under the conditions of a bead loading of 70% and a rotation number of 5,000 rpm.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus until Antox MS-60/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator, a nitrogen inlet tube and an ultrasonic wave generator and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 1.5 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment of the present invention.
  • the volume average particle diameter of the encapsulated pigment in the liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 180 nm.
  • the resulting liquid dispersion was dried at room temperature to obtain a solid matter, and the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined by thermally analyzing the solid matter with use of a thermal scanning calorimeter (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd.), and found to be 46°C.
  • a thermal scanning calorimeter differential scanning calorimeter: DSC
  • DSC200 trade name, manufactured by Seiko Instruments & Electronics Ltd.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus to such an extent of causing no bubbling in the permeated liquid, thereby adjusting the solid content concentration to 10 wt%.
  • the obtained pigment liquid dispersion was subjected to thermogravimetric measurement, and the adsorbed amount of the anionic polymerization surfactant, AQUALON KH-10, was determined from the weight loss value, as a result, KH-10/pigment was 25.6/100.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator and a nitrogen inlet tube and after elevating the internal temperature of the reaction vessel to 80°C, an aqueous solution prepared by dissolving 0.75 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 5 hours while introducing nitrogen into the reaction vessel. After the completion of polymerization, the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment "MCP17" of the present invention.
  • the volume average particle diameter of the obtained liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 145 nm.
  • the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined according to the Fox formula from the kinds and ratio of the monomer components constituting the polymer and found to be 18°C.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus to such an extent of causing no bubbling in the permeated liquid, thereby adjusting the solid content concentration to 10 wt%.
  • the obtained pigment liquid dispersion was subjected to thermogravimetric measurement, and the adsorbed amount of the anionic polymerization surfactant, AQUALON KH-10, was determined from the weight loss value, as a result, KH-10/pigment was 25.6/100.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator and a nitrogen inlet tube and after elevating the internal temperature of the reaction vessel to 80°C, an aqueous solution prepared by dissolving 0.23 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 5 hours while introducing nitrogen into the reaction vessel. After the completion of polymerization, the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment "MCP18" of the present invention.
  • the volume average particle diameter of the obtained liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 110 nm.
  • the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined according to the Fox formula from the kinds and ratio of the monomer components constituting the polymer and found to be 18°C.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus to such an extent of causing no bubbling in the permeated liquid, thereby adjusting the solid content concentration to 10 wt%.
  • the obtained pigment liquid dispersion was subjected to thermogravimetric measurement, and the adsorbed amount of the anionic polymerization surfactant, AQUALON KH-10, was determined from the weight loss value, as a result, KH-10/pigment was 25.6/100.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator and a nitrogen inlet tube and after elevating the internal temperature of the reaction vessel to 80°C, an aqueous solution prepared by dissolving 0.23 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 5 hours while introducing nitrogen into the reaction vessel. After the completion of polymerization, the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment "MCP19" of the present invention.
  • the volume average particle diameter of the obtained liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 110 nm.
  • the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined according to the Fox formula from the kinds and ratio of the monomer components constituting the polymer and found to be 18°C.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus to such an extent of causing no bubbling in the permeated liquid, thereby adjusting the solid content concentration to 10 wt%.
  • the obtained pigment liquid dispersion was subjected to thermogravimetric measurement, and the adsorbed amount of sodium dodecylbenzenesulfonate as an anionic surfactant was determined from the weight loss value, as a result, sodium dodecylbenzenesulfonate/pigment was 25/100.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator and a nitrogen inlet tube and after elevating the internal temperature of the reaction vessel to 80°C, an aqueous solution prepared by dissolving 0.23 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 5 hours while introducing nitrogen into the reaction vessel. After the completion of polymerization, the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment "MCP20" of the present invention.
  • the volume average particle diameter of the obtained liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 80 nm.
  • the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined according to the Fox formula from the kinds and ratio of the monomer components constituting the polymer and found to be 18°C.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus to such an extent of causing no bubbling in the permeated liquid, thereby adjusting the solid content concentration to 10 wt%.
  • the sulfur content in the obtained pigment liquid dispersion was determined by a flask combustion method and from the value obtained, the adsorbed amount of sodium dodecylbenzenesulfonate as an anionic surfactant was determined, as a result, sodium dodecylbenzenesulfonate/pigment was 13/100.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator and a nitrogen inlet tube and after elevating the internal temperature of the reaction vessel to 80°C, an aqueous solution prepared by dissolving 0.23 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 5 hours while introducing nitrogen into the reaction vessel. After the completion of polymerization, the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment "MCP21" of the present invention.
  • the volume average particle diameter of the obtained liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 80 nm.
  • the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined according to the Fox formula from the kinds and ratio of the monomer components constituting the polymer and found to be 18°C.
  • the resulting mixed solution was subjected to a dispersion treatment for 5 hours by using a disperser, Eiger Motor Mill Model M250 (manufactured by Eiger Japan Co., Ltd.), under the conditions of a bead loading of 70% and a rotation number of 5,000 rpm.
  • the solution was ultrafiltered by a cross-flow process in an ultrafiltration apparatus to such an extent of causing no bubbling in the permeated liquid, thereby adjusting the solid content concentration to 10 wt%.
  • the sulfur content in the obtained pigment liquid dispersion was determined by a flask combustion method and from the value obtained, the adsorbed amount of the anionic polymerizable surfactant, AQUALON KH-10, was determined, as a result, KH-10/pigment was 13/100.
  • This mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator and a nitrogen inlet tube and after elevating the internal temperature of the reaction vessel to 80°C, an aqueous solution prepared by dissolving 0.23 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 5 hours while introducing nitrogen into the reaction vessel. After the completion of polymerization, the pH was adjusted to 8 with an aqueous 1 mol/liter potassium hydroxide solution, and coarse particles were then removed by filtration through a membrane filter having a pore size of 1 ⁇ m.
  • the residue was ultrafiltered by a cross-flow process in an ultrafiltration apparatus and concentrated to have a solid content concentration of 15 wt%, thereby obtaining a liquid dispersion of the encapsulated pigment "MCP22" of the present invention.
  • the volume average particle diameter of the obtained liquid dispersion was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. and found to be 100 nm.
  • the glass transition temperature of the encapsulating polymer of the encapsulated pigment particle was determined according to the Fox formula from the kinds and ratio of the monomer components constituting the polymer and found to be 18°C.
  • methyl ethyl ketone 250 g was charged into a flask and after elevating the temperature to 75°C with stirring under nitrogen sealing, a mixed solution containing 170 g of n-butyl methacrylate, 58 g of n-butyl acrylate, 35 g of 2-hydroxyethyl methacrylate, 35 g of acrylic acid and 20 g of a polymerization initiator, Perbutyl O, was added dropwise over 2 hours. Then, the reaction was further allowed to proceed for 15 hours to obtain a vinyl-based polymer solution.
  • a mixed solution containing 170 g of n-butyl methacrylate, 58 g of n-butyl acrylate, 35 g of 2-hydroxyethyl methacrylate, 35 g of acrylic acid and 20 g of a polymerization initiator, Perbutyl O, was added dropwise over 2 hours. Then, the reaction was further allowed to proceed for 15 hours to obtain a vinyl-based poly
  • the zirconia beads were removed by filtration to obtain a product in which a dispersion comprising a polymer having a carboxyl group neutralized with a base and a pigment was dispersed in water. While stirring this product at ordinary temperature, a 1 N hydrochloric acid was added until the resin was insolubilized and fixed to the pigment. At this time, the pH was from 3 to 5.
  • the aqueous medium containing the pigment having fixed thereto the polymer was filtered by suction and washed with water to obtain a wet cake. While stirring the wet cake with a disperser, an aqueous 10% NaOH solution was added until the pH of the dispersion became from 8.5 to 9.5. After continuing the stirring for 1 hour, ion-exchanged water was added to adjust the solid content concentration to 20%, thereby obtaining the encapsulated pigment "MCP13" of C.I. Pigment Red 122.
  • the unadsorbed AQUALON KH-10 was treated by ultrafiltration according to a cross-flow process until AQUALON KH-10/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • the unadsorbed AQUALON KH-10 was treated by ultrafiltration according to a cross-flow process until AQUALON KH-10/pigment became 25/100 (this value was determined from the solid content concentration and the pigment concentration), thereby adjusting the solid content concentration to 15 wt%.
  • the resulting mixed solution was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature regulator and a nitrogen inlet tube and after elevating the internal temperature of the reaction vessel to 80°C under irradiation of an ultrasonic wave for 30 minutes, an aqueous solution prepared by dissolving 1.5 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was added dropwise, and the polymerization reaction was performed at 80°C for 6 hours while introducing nitrogen into the reaction vessel.
  • the pH of the reaction mixture was adjusted to 8 with an aqueous 2 mol/liter potassium hydroxide solution, and the particle size distribution was measured by a laser Doppler system particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co., as a result, change in the particle diameter was not observed.
  • the temperature was elevated to 70°C in nitrogen purging and while keeping the internal temperature of the reaction vessel at 70°C, an aqueous solution prepared by dissolving 0.32 g of potassium persulfate as a polymerization initiator in 10 g of ion-exchanged water was added dropwise over 10 minutes.
  • the polymerization reaction was further performed for 5 hours to obtain a polymer emulsion.
  • the polymer particle concentration in the obtained polymer emulsion was adjusted to 32 wt% to obtain Polymer Emulsion A, and this Polymer Emulsion A obtained was coated on a flat plate to form a liquid film having a uniform thickness and then air-dried at 30°C to obtain a transparent resin film.
  • the transparent film obtained was thermally analyzed by using a thermal scanning-type refractometer (differential scanning calorimeter: DSC), DSC200 (trade name, manufactured by Seiko Instruments & Electronics Ltd., as a result, the glass transition temperature of the polymer particle in Polymer Emulsion A was 0°C. Also, the volume average particle diameter of the polymer particle contained in Polymer Emulsion A as measured by a dynamic light-scattering particle size distribution analyzer, Microtrac UPA150 (trade name), manufactured by Leads & Northlop Co. was 40 nm.
  • Glycerin (15 g), 5 g of triethylene glycol monobutyl ether, 2 g of 1,2-hexanediol, 5 g of trimethylolpropane, 1 g of 2-pyrrolidone, 1 g of OLFINE E1010, 0.05 g of PROXEL XL-2 and 36.65 g of ion-exchanged water were mixed, and 1 g of potassium hydroxide in a concentration of 10 wt% was further added thereto and mixed to obtain a liquid mixture. This liquid mixture was added to 33.3 g of a liquid dispersion of MCP1, and the pigment was dispersed by using a stirring apparatus to obtain the objective Ink 1.
  • Inks 2 to 12, Inks 29 to 34, and Comparative Inks 1 and 2 each was prepared according to the method employed above for the preparation of Ink 1 based on the composition shown in Tables 1 to 4 below.
  • Table 1 Ink Composition Ink 1 Ink 2 Ink 3 Ink 4 Encapsulated Pigment MCP1 5 MCP2 5 MCP5 5 MCP6 5 Wetting Agent glycerin 15 15 15 15 15 15 15 Penetrant diethylene glycol monobutyl ether 5 5 triethylene glycol monobutyl ether 5 5 1,2-hexanediol 2 2 2 2 2 Solid wetting agent trimethylolpropane 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Polar solvent 2-pyrrolidone 1 1 1 1 Surfactant Olfine E1010 1 1 1 1 1 1 pH Adjusting agent potassium hydroxide 0.1 0.1 0.1 0.1 0.1 Antiseptic Proxel XL-2 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Water ion-exchanged water bal. bal. bal. bal.
  • Table 2 Ink Composition Ink 5 Ink 6 Encapsulated Pigment MCP1 5 MCP2 5 Fine polymer particle Polymer Emulsion A 4 4 Wetting Agent glycerin 15 15 Penetrant diethylene glycol monobutyl ether 5 triethylene glycol monobutyl ether 5 1,2-hexanediol 2 2 Solid wetting agent trimethylolpropane 5 5 Polar solvent 2-pyrrolidone 1 1 Surfactant Olfine E1010 1 1 1 pH Adjusting agent potassium hydroxide 0.1 0.1 Antiseptic Proxel XL-2 0.05 0.05 Water ion-exchanged water bal. bal.
  • Table 4 Ink Composition Comparative Ink 7 Comparative Ink 8 Encapsulated Pigment MCP13 5 Pigment Liquid Dispersion A 5 Wetting Agent glycerin 15 15 Penetrant diethylene glycol monobutyl ether 5 triethylene glycol monobutyl ether 5 1,2-hexanediol 2 2 Solid wetting agent trimethylolpropane 5 5 Polar solvent 2-pyrrolidone 1 1 Surfactant Olfine E1010 1 1 1 pH Adjusting agent potassium hydroxide 0.1 0.1 Antiseptic Proxel XL-2 0.05 0.05 Water ion-exchanged water bal. bal.
  • Inkjet Printer EM-930C trade name, manufactured by Seiko Epson Corp.
  • KOTAKU trade name, produced by Seiko Epson Corp.
  • the specular gloss on the recording surface at an incident angle 45° was measured under the conditions of 12 V, 50 W, an incident beam aperture diameter of 1 mm, a reflected light aperture diameter of 1.5 mm, an ND10 filter, an indent angle of 45°, a flapping angle of 0° and a standard mirror plate of 42.5.
  • the results obtained are evaluated according to the following criteria.
  • Inks 1 to 12, Inks 29 to 34, and Comparative Inks 1 and 2 prepared above each was filled in an ink cartridge, the ink cartridge was loaded on Inkjet Printer PX-600C (product name, manufactured by Seiko Epson Corp.), solid printing at 100% duty was performed in the region of 10 mm x 10 mm on SUPERFINE SPECIAL GLOSS FILM (trade name, produced by Seiko Epson Corp.), and the printed matter was left standing at a temperature of 25°C for 1 hour.
  • Inkjet Printer PX-600C product name, manufactured by Seiko Epson Corp.
  • solid printing at 100% duty was performed in the region of 10 mm x 10 mm on SUPERFINE SPECIAL GLOSS FILM (trade name, produced by Seiko Epson Corp.)
  • the printed matter was left standing at a temperature of 25°C for 1 hour.
  • the printed region was rubbed with an aqueous yellow fluorescent marker pen, ZEBRA PEN 2 (trademark, produced by ZEBRA) under a load of 500 g on the pen tip at a speed of 10 mm/sec, and whether staining was generated in the printed region was observed.
  • ZEBRA PEN 2 trademark, produced by ZEBRA
  • Inks 1 to 12, Inks 29 to 34, and Comparative Inks 1 and 2 prepared above each was filled in an ink cartridge, the ink cartridge was loaded on Inkjet Printer PX-600C (manufactured by Seiko Epson Corp.), 1-mm ruled lines were printed on a superfine special gloss paper sheet produced by Seiko Epson Corp., and the state of printing such as dot missing and slippage in the ink landing position was observed with an eye and evaluated according to the following criteria.
  • Inks 1 to 12, Inks 29 to 34, and Comparative Inks 1 and 2 prepared above each was filled in an ink cartridge, the ink cartridge was loaded on Inkjet Printer PX-600C (manufactured by Seiko Epson Corp.), solid printing was performed on plain paper, Xerox P (produced by Xerox Corp.), the density in this solid-printed portion was measured by a spectrophotometer (GRETAG SPM-50, manufactured by Gretag Macbeth), and the results obtained were evaluated according to the following criteria.
  • Table 5 the results when the encapsulated product (encapsulated pigment) of the present invention was used as an ink for inkjet recording are shown. It is seen that the ink compositions according to Inks 2, 29, 30, 31 and 34 have excellent ejection stability and the image printed on the inkjet special media is assured of high gloss and high image clarity and excellent in the scratch resistance and water resistance, and further that the image printed on plain paper has a high print density.
  • the ink compositions according to Inks 5 and 6 containing a polymer emulsion have high image clarity and excellent scratch resistance and the image printed on plain paper is assured of high print density. Particularly, the scratch resistance is excellent.
  • Inks 17 to 26 and Comparative Inks 3 to 8 each was prepared according to the method employed above for the preparation of Inks 1 to 12, Inks 29 to 34, and Comparative Inks 1 and 2, based on the composition shown in Tables 6 to 8 below.
  • DMH-20 is a compound of formula (1) and has the following structure produced by Nippon Nyukazai Co., Ltd.
  • butyl ethyl propane diol is a compound of formula (1) and has the following structure produced by Kyowa Hakko Chemical Co., Ltd.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
EP20050795833 2004-10-18 2005-10-18 Encapsulation product, process for producing the same, and ink composition Not-in-force EP1808225B1 (en)

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US20090062462A1 (en) 2009-03-05
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WO2006043571A1 (ja) 2006-04-27
JP5245252B2 (ja) 2013-07-24
US8524803B2 (en) 2013-09-03

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